Microdevice having multilayer structure and method for fabricating the same

ABSTRACT

The present invention provides a method of manufacturing a microdevice having a fine capillary cavity formed as a cut portion of a very thin layer which is likely to be broken, particularly a method of manufacturing a microdevice having complicated passages formed in three dimensions with high productivity. Also, the present invention provides a multi-functional microdevice which has a fine capillary passage formed by laminating plural resin layers, fine capillary cavities piercing through the respective layers to communicate and intersect three-dimensionally with each other, a space which should serve as a reaction chamber, a diaphragm valve, and a stopper structure. The method includes the steps of forming a semi-cured coating film having a cut portion made of an active energy ray curable composition on a coating substrate, laminating the semi-cured coating film with another member and removing the substrate, irradiating the semi-cured coating film again with an active energy ray before and/or after the removal of the substrate, thereby curing the coating film and bonding with said another member. The microdevice has a multi-layered structure wherein a member (J′) {selected from a member having a cut portion piercing through the member, a member having a recessed cut portion on the surface, and a member having a cut portion piercing through the member and a recessed cut portion on the surface}, a member (K′) and one or more active energy ray curable resin layers (X′) having a cut portion at a portion of the layer, the cut portion having a minimum width within a range from 1 to 1000 μm, are laminated and two or more cut portions in the members are connected to form a cavity.

TECHNICAL FIELD

[0001] The present invention relates to a method of manufacturingmicrodevices, for example, microfluidic device having a microfluidpassage therein, a microreaction device (microreactor) which is to beused in extensive fields such as chemistry, biochemistry, and physicalchemistry, or microprobe analytical device having a microcavity thereinand a structure such as fluid passage, reaction chamber, electrophoresiscolumn, membrane separation mechanism or sensor formed in a member,which is useful as an integrated DNA analytical device,microelectrophoresis device or microchromatography device; and relatesto microdevices obtained by the method.

[0002] More particularly, the present invention relates to amicrodevice, which has a laminated structure comprising an active energyray curable resin layer, the active energy ray curable resin layerhaving a cut portion of the resin in the layer, and has a fine capillarypassage formed by laminating plural resin layers, the cut portionspiercing through the respective layers to communicate with each other, aspace which should serve as a reaction chamber, a diaphragm valve and astopper structure.

[0003] The microdevice of the present invention is a microdevicecomprising an active energy ray curable resin layer containing ahydrophobic radiation polymerizable compound (a) and an amphipathicpolymerizable compound (b), which is copolymerizable with thehydrophobic radiation polymerizable compound, and the microdevice isless likely to adsorb a biological component.

[0004] Furthermore, the present invention relates to a method ofmanufacturing a microdevice, which comprises forming an active energyray curable resin layer on a coating substrate, laminating the activeenergy ray curable resin layer having a resin cut portion formed bypatterning exposure and development with another member in a semi-curedstate, irradiating again with an active energy ray, thereby bonding theactive energy ray curable resin layer with the another member and curingthe active energy ray curable resin layer, and removing the coatingsubstrate before, after, or during further irradiation with an activeenergy ray.

BACKGROUND ART

[0005] It has been known that fine grooves may be formed by an etchingmethod using a base material such as silicon, quartz, glass or polymerto manufacture a liquid passage or a separation gel channel (forexample, R. M. McCormick et al., “Analytical Chemistry”, page 2626, Vol.69, 1997), and that a cover such as a glass plate is used in a state ofbeing fixed by screw-fastening, fusion, or bonding for the purpose ofpreventing vaporization of a liquid during the operation.

[0006] However, fixation by screw-screw-fastening is likely to causeleakage of a liquid between laminated base materials or between the basematerial and the cover, while fusion and bonding require a very longtime, resulting in extremely poor productivity. According to thematerial and method, it is difficult to form a microdevice having amulti-layered structure wherein passages and other void portions areformed continuously in three layers, and it is considerably difficult toform a microdevice wherein numerous fragile thin layers are laminated.

[0007] Also, the journal of “SCIENCE” (Vol. 288, page 113, 2000)discloses a method of forming a silicone rubber member having grooves onthe surface using a casting method, interposing a silicone rubber sheetbetween two members and bonding them to form capillary passages whichthree-dimensionally intersect.

[0008] However, these two passages are independent passages and it wasimpossible to form thin capillary passages which pierce through therespective layers to communicate with each other. It was particularlyimpossible to industrially manufacture a microdevice having amulti-layered structure composed of a layer, which is too thin tosupport itself, using a flexible material and it was also impossible tomanufacture a microdevice which can perform complicated reaction andanalysis processes. Furthermore, there was a drawback in that theapplication is limited because the silicone rubber considerably adsorbsthe biological substance and it requires a long time to cure thesilicone rubber, resulting in extremely low productivity.

[0009] A microdevice formed of an active energy ray curable resin can bemanufactured with very high productivity because bonding can beperformed by a method of bringing an active energy ray curable resininto contact with another member in a semi-cured state and irradiatingagain with an active energy ray in that state, thereby completely curingthe resin, without using an adhesive.

[0010] However, according to this method, it was difficult to laminatenumerous films having a cut portion, which are too thin to supportthemselves while aligning the microcut portions from an industrial pointof view. Particularly, in the case in which the cut portion of the resinlayer is in the form of a continuous line, a curve or numerous lines, itbecomes more difficult to handle the film. A method of forming capillarypassages, which pierce through the respective layers to communicate witheach other, is heretofore not known. Also, there is no known microdeviceobtained by laminating three or more films each having a cut portion,which are made of an active energy ray curable resin and are too thin tosupport themselves, while aligning the microcut portions.

DISCLOSURE OF INVENTION

[0011] An object to be solved by the present invention is to provide amethod of manufacturing a microdevice having a fine capillary cavityformed as a cut portion of a very thin layer which is likely to bebroken, particularly a method of manufacturing a microdevice havingcomplicated passages formed in three dimensions with high productivity,and to provide a multi-functional microdevice which has a fine capillarypassage formed by laminating plural resin layers, fine capillarycavities piercing through the respective layers to communicate andthree-dimensionally intersect with each other, a space which shouldserve as a reaction chamber, a diaphragm valve, and a stopper structure.

[0012] The present inventors have intensively researched the methods ofachieving the above object and found that a microdevice having a cavityformed therein, particularly a microdevice comprising plural layerslaminated continuously can be manufactured by forming a semi-curedcoating film having a cut portion made of an active energy ray curablecomposition on a coating substrate, laminating the semi-cured coatingfilm with another member and removing the substrate, irradiating thesemi-cured coating film again with an active energy ray before and/orafter the removal of the substrate, thereby curing the coating film andbonding with said another member. Thus, the present invention has beencompleted.

[0013] The present invention provides a method of manufacturing amicrodevice having a laminated structure comprising one or more resinlayers (X) having a cut portion, said resin layers being laminated withanother member or another resin layer (X) to form a cavity composed ofthe cut portion, said method comprising:

[0014] (i) the step (i) of applying an active energy ray curablecomposition (x) containing a radiation polymerizable compound (a) on acoating substrate to form an uncured coating film,

[0015] (ii) the step (ii) of irradiating the uncured coating film otherthan the portion, which should serve as the cut portion, with an activeenergy ray, thereby making the uncured coating film of the irradiatedportion non-flowable or slightly flowable, and semi-curing to such anextent that unreacted active energy ray polymerizable functional groupsremain to form a semi-cured coating film,

[0016] (iii) the step (iii) of removing the uncured composition (x) ofthe non-irradiated portion from the semi-cured coating film to obtain asemi-cured coating film having a cut portion of the coating film,

[0017] (iv) the step (iv) of laminating the semi-cured coating filmhaving a cut portion with another member (J) to form a resin layer (X),

[0018] (v) the step (v) of removing the coating substrate from the resinlayer (X), thereby transfering the resin layer (X) onto the member (J),and

[0019] (vi) the step (vi) of irradiating the resin layer (X) in asemi-cured state with an active energy ray, thereby further curing theresin later (X) and bonding the resin layer (X) with the member (J)after the step (iv) and before and/or after the step (v).

[0020] The present invention provides a method of manufacturing amicrodevice, wherein the removal of the coating substrate in the step(v) is removal by dissolution of the coating substrate, or the step (vi)is provided before the step (v) and the removal of the coating substratein the step (v) is performed by peeling, and a method of manufacturing amicrodevice, wherein, after performing the steps (i), (ii), (iii), (iv)and (v), or the steps (i), (ii), (iii), (iv), (v) and (vi), or the steps(i), (ii), (iii), (iv), (vi) and (v) in this order, the steps (i) to (v)or the steps (i) to (vi) are repeated using the member (J) laminatedwith the resin layer (x) in place of the member (J) in the step (iv),thereby laminating plural resin layers (X).

[0021] The present invention provides a method of manufacturing amicrodevice, wherein plural resin layers (X) are laminated so that atleast the cut portions are partially laid one upon another to form acavity composed of the connected cut portions of plural resin layers (X)in a laminate. The present invention provides a method of manufacturinga microdevice, wherein the member (J) is a member having a cut portionpiercing through the member, or a member having a recessed cut portionon the surface, or a member having a cut portion piercing through themember and a recessed cut portion on the surface, and the member (J) andthe resin layer (X) are laminated so that at least the cut portion ofthe member (J) and the cut portion of the resin layer (X) are partiallylaid one upon another to form a cavity composed of the cut portion ofthe member (J) and the cut portion of the resin layer (X), which areconnected with each other, in a laminate.

[0022] The present invention provides a method of manufacturing amicrodevice, wherein, between the step (i) and the step (ii) and/orbetween the step (ii) and the step (iii) and/or between the step (iii)and the step (iv), a portion of the resin layer (X) is irradiated withan active energy ray, thereby partially curing the resin layer so thatthe irradiated portion is not bonded with another member in the step(iv) to form a portion, which is not bonded but is contacted with theanother member or resin layer, in the resin layer (X).

[0023] The present invention provides a method of manufacturing amicrodevice wherein irradiation with the active energy ray in the step(ii) is performed in the shape for forming a stopper to provide aportion of the resin layer (X) with a structure, which serves as thestopper, and the portion subjected to partial curing is a portion whichserves as the stopper of the resin layer (X).

[0024] The present invention provides a method of manufacturing amicrodevice, wherein the active energy ray curable composition (x)contains a hydrophobic radiation polymerizable compound (a) whosehomopolymer exhibits a contact angle with water of 60 degrees or more,and an amphipathic polymerizable compound (b) which is copolymerizablewith the hydrophobic radiation polymerizable compound.

[0025] Furthermore, the present invention provides a microdevice havinga laminated structure comprising a member (J′) {selected from a memberhaving a cut portion piercing through the member, a member having arecessed cut portion on the surface, and a member having a cut portionpiercing through the member and a recessed cut portion on the surface},one or more active energy ray curable resin layers (X′) having a cutportion at a portion of the layer, the cut portion having a minimumwidth within a range from 1 to 1000 μm, and a member (K′) {selected froma member having a cut portion piercing through the member, a memberhaving a recessed cut portion on the surface, and a member having a cutportion piercing through the member and a recessed cut portion on thesurface}, which are laminated, while two or more cut portions in themembers are connected to form a cavity.

[0026] The present invention provides a microdevice wherein one or moremembers selected from the member (J′), the resin layer (X′) and themember (K′) has one or more linear cavity provided parallel to thelaminated surface of the members, or a microdevice wherein a portion ofthe cavity is a fluid passage and plural passages formed in differentresin layers (X′) or branched passages intersect three-dimensionallyacross the resin layer (X′).

[0027] The present invention provides a microdevice which has a portionthat is not bonded but is contacted with another member laminatedadjacent to a portion of one or more members selected from the member(J′), the resin layer (X′) and the member (K′).

[0028] The present invention provides a microdevice wherein a portion ofat least one resin layer (X′) is provided with a structure, which servesas a stopper by replacing a portion of the peripheral portion by a cutportion and the portion, which is not bonded but is contacted withanother member laminated adjacent thereto, is the stopper.

[0029] The present invention provides a microdevice wherein at least onemember selected from the member (J′), the resin layer (X′) and themember (K′) is directly laminated with a member, which serves as adiaphragm, at one surface and is directly laminated with another memberhaving a cut portion at the other surface, and the cut portions form acavity by lamination, while another member laminated on the back surfaceof the member, which serves as the diaphragm, has orifice-shaped cutportions, which serve as an inlet and/or an outlet to the cavity, atleast one of the inlet and the outlet being formed across the memberfrom the diaphragm, and the peripheral portion does not contact with thediaphragm and the passage can be closed by deforming the diaphragm tocontact with the peripheral portion of at least one of the inlet and theoutlet.

[0030] The present invention provides a microdevice wherein the activeenergy ray curable composition contains an amphipathic radiationpolymerizable compound which is copolymerizable with a radiationpolymerizable compound, or a microdevice wherein a member (J′) {selectedfrom a member having a cut portion piercing through the member, a memberhaving a recessed cut portion on the surface, and a member having a cutportion piercing through the member and a recessed cut portion on thesurface), one or more active energy ray curable resin layers (X′) havinga cut portion at a portion of the layer, the cut portion having aminimum width within a range from 1 to 1000 μm, and a member (K″) havingno cut portion, which serves as a diaphragm, are laminated and themember (K″) has a portion, which is not bonded but is contacted withanother member laminated adjacent thereto, the portion being a diaphragmportion, while two or more cut portions in the member (J′) and the resinlayer (X′) are connected to form a cavity, and a microdevicemanufactured by a manufacturing method according to the presentinvention described above.

BRIEF DESCRIPTION OF DRAWINGS

[0031]FIG. 1 is a plan view schematically showing a coating substrateand a resin layer (X-1) used in Example 1 and Example 3 viewed from adirection perpendicular to the surface.

[0032]FIG. 2 is a plan view schematically showing a microdevice of thepresent invention manufactured in Example 1 and Example 3.

[0033]FIG. 3 is a partially enlarged elevation view schematicallyshowing a microdevice of the present invention manufactured in Example 1and Example 3.

[0034]FIG. 4 is a plan view schematically showing a coating substrateand a resin layer (X′-4-1) used in Example 4.

[0035]FIG. 5 is a plan view schematically showing a coating substrateand a resin layer (X′-4-2) used in Example 4.

[0036]FIG. 6 is a plan view schematically showing a coating substrateand a resin layer (X′-4-3) used in Example 4.

[0037]FIG. 7 is a plan view schematically showing a microdevicemanufactured in Example 4.

[0038]FIG. 8 is a sectional view taken along line A-A of FIG. 7, whichschematically shows a microdevice manufactured in Example 4.

[0039]FIG. 9 is a plan view schematically showing a microdevicemanufactured in Example 5.

[0040]FIG. 10 is a sectional view taken along line A-A of FIG. 9, whichschematically shows a microdevice manufactured in Example 5.

[0041]FIG. 11 is a plan view schematically showing a member (J′-8-1)manufactured in Example 8 viewed from a direction perpendicular to thesurface on which a cut portion is formed.

[0042]FIG. 12 is a plan view schematically showing a resin layer(X′-8-1) and a resin layer (X′-8-3) manufactured in Example 8.

[0043]FIG. 13 is a plan view schematically showing a resin layer(X′-8-2) manufactured in Example 8.

[0044]FIG. 14 is a view schematically showing a resin layer (X′-8-4)manufactured in Example 8.

[0045]FIG. 15 is a plan view schematically showing an intermediate layer(diaphragm layer) manufactured in Example 8.

[0046]FIG. 16 is a plan view schematically showing a member (K′-8)manufactured in Example 8 viewed from a direction perpendicular to thesurface on which a cut portion is formed.

[0047]FIG. 17 is a plan view schematically showing a microdevicemanufactured in Example 8.

[0048]FIG. 18 is a sectional view taken along line A-A of FIG. 17, whichschematically shows a microdevice manufactured in Example 8.

BEST MODE FOR CARRYING OUT THE INVENTION

[0049] The method of the present invention relates to a method ofmanufacturing a microdevice, which comprises laminating and bonding oneresin layer having a resin cut portion (hereinafter, such a resin layeris referred to as a “resin layer (X)”) or two or more resin layers (X)having passages each having the same or different shape as anothermember and laminating the resin layer (X) with another member or anotherresin layer (X), and thus the cut portion forms a cavity.

[0050] The coating substrate used in the method of the present inventioncan be coated with an active energy ray curable composition (x)(hereinafter occasionally abbreviated to a “composition (x)”) and can beremoved after curing the composition (x). In the present invention,coating includes casting and the coating film includes cast articles.

[0051] It is not necessary to specifically limit the shape of thecoating substrate, and the coating substrate can take any form accordingto the purpose. For example, the coating substrate can be in the form ofsheet (including film, ribbon and belt), plate, roll (obtained by usinga large roll as the coating substrate and performing the steps ofcoating, semi-curing, lamination and peeling during the roll rotates onetime) and molded article or mold having a complicated shape. In view ofease of coating of the active energy ray curable composition (x) thereonand ease of irradiation with an active energy ray, the surface to bebonded is preferably in the form of a plane or secondary curved surface,and is particularly preferably a pliable sheet. In view of theproductivity, it is preferably in the form of a roll.

[0052] The coating substrate may be provided with measures, figures, andaligning symbols printed on the surface. The material of the coatingsubstrate is not specifically limited as long as it satisfies the aboveconditions, and examples thereof include polymer, glass, crystal such asquartz, ceramic, semiconductor such as silicon, metal, paper, nonwovenfabric and woven fabric. Among these materials, polymer and metal areparticularly preferred.

[0053] The polymer used as the coating substrate may be a homopolymer ora copolymer, or may be a thermoplastic polymer or a thermosettingpolymer. In view of the productivity, the polymer used as the coatingsubstrate is preferably a thermoplastic polymer or active energy raycurable polymer.

[0054] In the case in which the coating substrate is removed by peelingusing a mechanical force, as the material which is not easily dissolvedin various active energy ray curable compositions (x) and is easilypeeled off from the cured article thereof, polyolefin polymer,chlorine-containing polymer, fluorine-containing polymer, polythioetherpolymer, polyether ketone polymer and polyester polymer are preferablyused.

[0055] In the case in which the coating substrate is removed bydissolution, for example, there can be preferably used water-solubleresin such as polyvinyl pyrrolidone, polyethylene glycol, polyvinylalcohol or acrylic copolymer; lower alcohol-soluble resin having apolyether group such as polyethylene glycol group and a hydroxyl group;alkali-soluble resin such as carboxyl group-, phosphoric acid group- orsulfone group-containing resin; and acid-soluble resin such as aminogroup- or quaternary ammonium salt-containing resin.

[0056] The coating substrate may be composed of a polymer blend or apolymer alloy, or may be a laminate or a composite. Furthermore, thecoating substrate may contain additives such as modifiers, colorants,fillers and reinforcers.

[0057] The coating substrate may be surface-treated in the case of thepolymer and other materials. The surface treatment may be performed forthe purpose of prevention of dissolution by the composition (x), ease ofpeeling of the composition (x) from the cured article, improvement inwettability of the composition (x) and prevention of contamination withthe composition (x).

[0058] The surface treatment of the coating substrate may be performedby any method and examples thereof include corona treatment, plasmatreatment, flame treatment, acid or alkali treatment, sulfonationtreatment, fluorination treatment, primer treatment with silane couplingagent, surface graft polymerization, coating of surfactants andreleasants, and physical treatment such as rubbing or sand blasting.

[0059] In the case in which an active energy ray curable composition (x)is applied on the coating substrate in a small thickness, the coatingsubstrate is preferably wetted with the composition (x) or preferablyhas a weak repellency. That is, a contact angle with the composition (x)is preferably 90 degrees or less, more preferably 45 degrees or less,still more preferably 25 degrees or less, and most preferably 0 degree.

[0060] In the case in which the coating substrate is a material having alow surface energy, for example, polyolefin, fluorine polymer,polyphenylene sulfide or polyether ether ketone, the contact angle withthe composition (x) is preferably reduced by the surface treatment ofthe bonding surface of the coating substrate.

[0061] However, it is necessary to control the degree of the treatmentto prevent the active energy ray curable composition (x) cured by thesurface treatment from being bonded too firmly to peel off. As thesurface treatment for improvement of the wettability, for example,corona discharge treatment, plasma treatment, acid or alkali treatment,sulfonation treatment, primer treatment and coating of surfactants arepreferred.

[0062] In the case in which the coating substrate is formed of amaterial which has good adhesion, thereby making it difficult to peel acured article of the active energy ray curable composition (x), thesurface treatment such as fluorination treatment, coating of fluorine orsilicone releasants or introduction of a hydrophilic group orhydrophobic group by a surface graft method is preferred. In the case inwhich the coating substrate is a porous material such as paper, nonwovenfabric, or knitted woven fabric, the coating substrate is preferablysubjected to a fluorine compound treatment or made non-porous by coatingin order to prevent contamination with the composition (x). Also, thewettability can be controlled by selecting modifiers to be blended withthe coating substrate, in addition to the surface treatment.

[0063] Examples of the modifier, which can be mixed with the coatingsubstrate, include hydrophobizing agents (water repellents) such assilicone oil or fluorine-substituted hydrocarbon; hydrophilizing agentssuch as water-soluble polymer, surfactant, inorganic powders (e.g.silica gel); and plasticizers such as dioctyl phthalate. Examples of thecolorant, which can be mixed with the coating substrate, include anydyes or pigments, fluorescent dyes or pigments, and ultravioletabsorbers. Examples of the reinforcer, which can be mixed with thecoating substrate, include inorganic powders such as clay; and inorganicand organic fibers or fabrics.

[0064] The radiation polymerizable compound (a) (hereinafteroccasionally abbreviated to “compound (a)”) used in the presentinvention may be any radical polymerizable, anion polymerizable orcation polymerizable compound as long as it is polymerized and cured byirradiation with an active energy ray. The compound (a) is not limitedto a compound which is polymerized in the absence of a polymerizationinitiator, and a compound which is polymerized by irradiation with anactive energy ray only in the presence of the polymerization initiator.

[0065] The compound (a) is preferably an addition-polymerizable compoundbecause of high polymerization rate, more preferably a compound having apolymerizable carbon-carbon double bond as an active energy raypolymerizable functional group, and particularly preferably a(meth)acrylate compound and vinyl ethers, which have high reactivity,and a maleimide compound which is cured even in the absence of thephotopolymerization initiator.

[0066] Furthermore, the compound (a) is preferably a compound, which ispolymerized to form a crosslinked polymer, because it exhibits highshape retention in a semi-cured state and also exhibits high strengthafter curing. Therefore, a compound having two or more polymerizablecarbon-carbon double bonds in a molecule (hereinafter “possession of twoor more polymerizable carbon-carbon double bonds in a molecule” isoccasionally referred to as “polyfunctional”) is more preferred.

[0067] Examples of the polyfunctional (meth)acrylate monomer, which canbe preferably used as the compound (a) include difunctional monomer suchas diethylene glycol di(meth)acrylate, neopentyl glycoldi(meth)acrylate, 1,6-hexanediol di(meth)acrylate,2,2′-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane,2,2′-bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane,hydroxydipivalate neopentyl glycol di(meth)acrylate, dicyclopentanyldiacrylate, bis(acryoxyethyl)hydroxyethyl isocyanurate orN-methylenebisacrylamide; trifunctional monomer such astrimethylolpropane tri(meth)acrylate, trimethylolethanetri(meth)acrylate, tris(acryloxyethyl) isocyanurate orcaprolactone-modified tris(acryloxyethyl) isocyanurate; tetrafunctionalmonomer such as pentarythritol tetra(meth)acrylate; and hexafunctionalmonomer such as dipentarythritol hexa(meth)acrylate.

[0068] As the compound (a), a polymerizable oligomer (includingprepolymer, the same as in the following case) can be used and includes,for example, a compound having a weight-average molecular weight withina range from 500 to 50000. Examples of the polymerizable oligomerinclude (meth)acrylate ester of epoxy resin, (meth)acrylate ester ofpolyether resin, (meth)acrylate ester of polybutadiene resin, andpolyurethane resin having a (meth)acryloyl group at a molecularterminal.

[0069] Examples of the maleimid compound (a) include difunctionalmaleimide such as 4,4′-metyhylenebis(N-phenyl maleimide),2,3-bis(2,4,5-trimethyl-3-thienyl)maleimide, 1,2-bis maleimideethane,1,6-bis maleimidehexane, triethylene glycol bis maleimide,N,N′-m-phenylene dimaleimide, m-tolylene dimaleimide, N,N′-1,4-phenylenedimaleimide, N,N′-diphenylmethane dimaleimide, N,N′-diphenyl etherdimaleimide, N,N′-diphenylsulfone dimaleimide, 1,4-bis(maleimideethyl)1,4-diazoniabicyclo-[2,2,2]octane dichloride or4,4′-isopropylidenediphenyl=dicyanate.N,N′-(methylenedi-p-phenylene)dimaleimide;and maleimide having a maleimide group and a polymerizable functionalgroup other than the maleimide group, such as N-(9-acridinyl)maleimide.The maleimide monomer can also be copolymerized with a compound having apolymerizable carbon-carbon double bond, such as vinyl monomer, vinylethers or acrylic monomer.

[0070] These compounds (a) can be used alone, or two or more kinds ofthem can be used in combination. The radiation polymerizable compound(a) can also be replaced by a mixture of a polyfunctional monomer and amonofunctional monomer for the purpose of controlling the viscosity andenhancing the adhesion and the tackiness in a semi-cured state.

[0071] Examples of the monofunctional (meth)acrylate monomer includemethyl methacrylate, alkyl (meth)acrylate, isobornyl (meth)acrylate,alkoxypolyethylene glycol (meth)acrylate, phenoxydialkyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, alkylphenoxy polyethyleneglycol (meth)acrylate, nonylphenoxy polypropylene glycol (meth)acrylate,hydroxyalkyl (meth)acrylate, glycerol acrylate methacrylate, butanediolmono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate,2-acryloyloxyethyl-2-hydroxypropyl acrylate, ethylene oxide-modifiedphthalic acid acrylate, w-carboxycaprolactone monoacrylate,2-acryloyloxypropylhydrogen phthalate, 2-acryloyloxyethylsuccinc acid,acrylic acid dimer, 2-acryloyloxypropylhexahydrohydrogen phthalate,fluorine-substituted alkyl (meth)acrylate, chlorine-substituted alkyl(meth)acrylate, sodium sulfonate ethoxy(meth)acrylate, sulfonicacid-2-methylpropane-2-acrylamide, phosphate ester group-containing(meth)acrylate, sulfonate ester group-containing (meth)acrylate, silanogroup-containing (meth)acrylate, ((di)alkyl)amino group-containing(meth)acrylate, quaternary ((di)alkyl)ammonium group-containing(meth)acrylate, (N-alkyl)acrylamide, (N,N-dialkyl)acrylamide andacryloylmorpholine.

[0072] Examples of the monofunctional maleimide monomer include N-alkylmaleimide such as N-methyl maleimide, N-ethyl maleimide, N-butylmaleimide or N-dodecyl maleimide; N-alicyclic maleimide such asN-cyclohexyl maleimide; N-benzyl maleimide; N-(substituted ornon-substituted phenyl) maleimide such as N-phenyl maleimide,N-(alkylphenyl)maleimide, N-dialkoxyphenyl maleimide,N-(2-chlorophenyl)maleimide, 2,3-dichloro-N-(2,6-diethylphenyl)maleimideor 2,3-dichloro-N-(2-ethyl-6-methylphenyl)maleimide; maleimide having ahalogen, such as N-benzyl-2,3-dichloro maleimide orN-(4′-fluorophenyl)-2,3-dichloro maleimide; maleimide having a hydroxylgroup, such as hydroxyphenyl maleimide; maleimide having a carboxygroup, such as N-(4-carboxy-3-hydroxyphenyl) maleimide; maleimide havingan alkoxyl group, such as Nmethoxyphenyl maleimide; maleimide having anamino group, such as N-[3-(diethylamino)propyl] maleimide; polycyclicaromatic maleimide such as N-(1-pyrenyl) maleimide; and maleimide havinga heterocycle, such as N-(dimethylamino4-methyl-3-coumarinyl)maleimideor N-(4-anilino-1-napthyl)maleimide.

[0073] In the case in which an amphipathic compound (b) describedhereinafter is added to the composition (x), a hydrophobic compound (a)is preferably use as the compound (a). The hydrophobic compound (a)refers to a compound whose homopolymer exhibits a contact angle withwater of 60 degrees or more. The hydrophobic compound (a) can be used byselecting from the compounds listed as the compound (a) and almost allof compounds listed are hydrophobic compounds (a).

[0074] The composition (x) is irradiated with an active energy ray toform a cured resin and contains a compound (a) as an essentialcomponent. The composition (x) may contain the compound (a) alone, ormay contain a mixture of plural kinds of compounds (a) . If necessary,other components can be added to the composition (x). Examples of theother component, which can be added to the composition (x), includecompounds, which are copolymerizable with the compound (a), activeenergy ray polymerization initiators, polymerization-delaying agents,polymerization inhibitors, thickeners, modifiers, colorants andsolvents.

[0075] The compound, which can be added to the composition (x) and iscopolymerizable with the compound (a), may be an amphipathic compound, ahydrophilic compound or a hydrophobic compound. The hydrophiliccompound, which can be added to the composition (x) and iscopolymerizable with the compound (a), has a hydrophilic group in themolecule and gives a hydrophilic polymer.

[0076] Examples of such a compound include vinyl pyrrolidone,N-substituted or non-substituted acrylamide, acrylic acid, polyethyleneglycol group-containing (meth)acrylate, hydroxyl group-containing(meth)acrylate, amino group-containing (meth)acrylate, carboxylgroup-containing (meth)acrylate, phosphoric acid group-containing(meth)acrylate, and sulfone group-containing (meth)acrylate.

[0077] The hydrophobic compound, which can be added to the composition(x) and is copolymerizable with the compound (a), has a hydrophobicgroup in the molecule and gives a hydrophobic polymer. Examples of sucha compound include alkyl (meth)acrylate, fluorine-containing(meth)acrylate and (alkyl-substituted)siloxane group-containing(meth)acrylate.

[0078] The amphipathic compound which can be added to the composition(x) and is copolymerizable with the compound (a) (hereinafter such acompound is referred to as an “amphipathic compound (b)” or is simplyreferred to as a “compound (b)”) is preferably a compound having one ormore polymerizable carbon-carbon unsaturated bonds in a molecule.Although it is not necessary that a homopolymer of the amphipathiccompound (b) be a crosslinked polymer, the amphipathic compound (b) maybe a compound which can be converted into a crosslinked polymer.

[0079] The amphipathic compound (b) and the hydrophobic compound (a)dissolve uniformly in each other. In this case, “dissolve” means thefact that macroscopic phase separation does not occur and also includesthe state where micelles are formed and stably dispersed.

[0080] As used herein, the amphipathic compound refers to a compoundwhich has a hydrophilic group and a hydrophobic group in the moleculeand is compatible with water and a hydrophobic solvent. Also in thiscase, “compatible” means the fact that macroscopic phase separation doesnot occur and also includes the state where micelles are formed andstably dispersed. Regarding the amphipathic compound (b), a solubilityin water at 0° C. is preferably 0.5% by weight or more and a solubilityin a mixed solvent of cyclohexane and toluene in a weight ratio of 5:1at 25° C. is preferably 25% by weight or more.

[0081] As used herein, the solubility, for example, the solubility of0.5% by weight or more means that at least 0.5% by weight of thecompound can be dissolved, but not include the fact that a very smallamount of the solvent can be dissolved in the compound, though 0.5% byweight of the compound is not dissolved in the solvent. When using acompound wherein either of the solubility in water or the solubility inthe mixed solvent of cyclohexane and toluene in a weight ratio of 5:1 islower than the value, it becomes difficult to satisfy both high surfacehydrophilicity and water resistance.

[0082] In the case in which the amphipathic compound (b) has a nonionichydrophilic group, particularly a hydrophilic group of polyether,balance between hydrophilicity and hydrophobic is preferably within arange from 10 to 16, and more preferably from 11 to 15, in terms of aGriffin's HLB value. When the HLB value is not within the above range,it is difficult to obtain a fabricated article having highhydrophilicity and excellent water resistance, or the combination ormixing ratio of the compound required to obtain the fabricated articleis extremely limited, resulting in unstable performances of thefabricated article.

[0083] The hydrophilic group of the amphipathic compound (b) is notspecifically limited and examples thereof include cation group such asamino group, quaternary ammonium group or phosphonium group; anion groupsuch as sulfone group, phosphoric acid group or carbonyl group; noniongroup, for example, polyether group such as hydroxyl group orpolyethylene glycol group, or amide group; and amphoteric ion group suchas amino acid group. The hydrophilic group is preferably a polyethergroup, and particularly preferably a polyethylene glycol chain of arepeating number of 6 to 20.

[0084] Examples of the hydrophobic group of the amphipathic compound (b)include alkyl group, alkylene group, alkylphenyl group, long chainalkoxy group, fluorine-substituted alkyl group and siloxane group. Theamphipathic compound (b) preferably contains, as the hydrophobic group,an alkyl or alkylene group having 6 to 20 carbon atoms. The compound mayhas the alkyl or alkylene group having 6 to 20 carbon atoms in the formof alkylphenyl group, alkylphenoxy group, alkoxy group or phenylalkylgroup.

[0085] The amphipathic compound (b) is preferably a compound which has apolyethylene glycol chain of a repeating number of 6 to 20 as thehydrophilic group and also has alkyl or alkylene group having 6 to 20carbon atoms as the hydrophobic group. The amphipathic compound (b),which can be used more preferably, may be a compound represented by thegeneral formula (1):

[0086] General Formula (1)

CH₂═CR¹COO (R²O)_(n)-φ-R³

[0087] (wherein R¹ represents hydrogen, a halogen atom or a lower alkylgroup, R² represents an alkylene group having 1 to 3 carbon atoms, nrepresents an integer of 6 to 20, φ represents a phenylene group, and R³represents an alkyl group having 6 to 20 carbon atoms).

[0088] More specifically, R³ is a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a dodecyl group or a pentadecylgroup, and preferably a nonyl group or a dodecyl group. In the generalformula (1), the larger the numerical value of n, the larger the numberof carbon atoms of R³, the better.

[0089] A relationship between the numerical value of n and the number ofcarbon atoms of R³ is preferably within a range from 10 to 16, andparticularly preferably from 11 to 15, in terms of a Griffin's HLBvalue. Among these amphipathic compounds (b), nonylphenoxy polyethyleneglycol (n=8 to 17) (meth)acrylate and nonylphenoxy polypropylene glycol(n=8 to 17) (meth)acrylate are particularly preferred.

[0090] The active energy ray polymerization initiator, which can beadded to the composition (x), is not specifically limited as long as itis active to an active energy ray used in the present invention and iscapable of polymerizing the compound (a) and may be, for example, aradical polymerization initiator, an anion polymerization initiator or acation polymerization initiator. The active energy ray polymerizationinitiator is particularly effective when using light rays as the activeenergy ray.

[0091] Examples of the photopolymerization initiator includeacetophenones such as p-tert-butyltrichloroacetophenone,2,2′-diethoxyacetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one;ketones such as benzophenone, 4,4′-bisdimethylaminobenzophenone,2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone and2-isopropylthioxanthone; benzoin ethers such as benzoin, benzoin methylether, benzoin isopropyl ether and benzoin isobutyl ether; benzyl ketalssuch as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone; andazide such as N-azidesulfoneylphenyl maleimide. Also, polymerizablephotopolymerization initiators such as maleimide compound can be listed.

[0092] When the photopolymerization initiator is mixed with thecomposition (x), the amount of the non-polymerizable photopolymerizationinitiator is preferably within a range from 0.005 to 20% by weight, andparticularly preferably from 0.1 to 5% by weight. Thephotopolymerization initiator may be a polymerizable compound, forexample, a polyfunctional or monofunctional maleimide monomer listed asthe radiation polymerizable compound (a). The amount is not limited tothe amount within the above range.

[0093] The polymerization-delaying agent, which can be added to thecomposition (x), include, for example, vinyl monomers having a lowerpolymerization rate than that of the radiation polymerizabie compound(a), such as styrene, α-methylstyrene, α-phenylstyrene, p-octylstyrene,p-(4-pentylcyclohexyl)styrene, p-phenylstyrene,p-(pethoxyphenyl)phenylstyrene, 2,4-diphenyl-4-methyl-1-pentene,4,4′-divinylbiphenyl and 2-vinyl naphthalene in the case in which theradiation polymerizable compound (a) is an acryloyl group-containingcompound.

[0094] The polymerization inhibitor, which can be added to thecomposition (x), includes, for example, hydroquinone derivatives such ashydroquinone and methoxyhydroquinone; and hindered phenols such asbutylhydroxytoluene, tert-butylphenol and dioctylphenol in the case inwhich the radiation polymerizable compound (a) is a polymerizablecarbon-carbon double bond-containing compound.

[0095] When using light rays as the active energy ray, thepolymerization-delaying agent and/or the polymerization inhibitor arepreferably used in combination with the photopolymerization initiator inorder to improve the patterning accuracy. Examples of the thickener,which can be added to the composition (x), include chain polymers suchas polystyrene.

[0096] Examples of the modifier, which can be added to the composition(x), include hydrophobic compounds, that function as a water repellentand a releasant, such as silicone oil and fluorine-substitutedhydrocarbon; water-soluble polymers, that function as a hydrophilizingagent and an adsorption inhibitor, such as polyvinyl pyrrolidone,polyethylene glycol and polyvinyl alcohol; and nonionic, anionic andcationic surfactants, which function as a wettability modifier, areleasant and an adsorption inhibitor. Examples of the colorant, whichcan be optionally mixed with the composition (x), include any dyes orpigments, fluorescent pigments and ultraviolet absorbers.

[0097] The solvent, which can be added to the composition (x), may beany solvent as long as it can dissolve the respective components of thecomposition (x) to yield a uniform solution, and is preferably avolatile solvent. In the case in which the composition (X) has a highviscosity or is applied in a small thickness, the solvent is preferablyadded to the composition (x) . The solvent is volatilized and removedafter coating or in any of the following steps.

[0098] According to the method of the present invention, the composition(x) is applied on a coating substrate to form an uncured coating film.This step is referred to as the “step (i)”. The thickness of the coatingfilm is not specifically limited, but is preferably 1 μm or more, morepreferably 5 μm or more, and still more preferably 10 μm or more. Whenthe thickness is less than the above range, it becomes difficult tomanufacture.

[0099] The thickness of the coating film is preferably 1000 μm or less,more preferably 400 μm or less, and still more preferably 200 μm orless. When the thickness is more than the above, range, the effects ofthe present invention are adversely affected. The thickness of thecoating film slightly varies due to shrinkage upon curing, but generallycorresponds to the thickness of the layer which serves as the resinlayer (X). The composition may be applied to any position, for example,the entire or partial surface of the coating substrate. Alternatively,the composition may be applied to a portion other than the portion whichis laminated with a member (J) described hereinafter.

[0100] As a method of applying the composition (x) to the coatingsubstrate, there can be employed any method capable of applying on thecoating substrate, and examples thereof include a spin coating method,roller coating method, casting method, dipping method, spraying method,bar coater method, X-Y applicator method, screen printing method,letterpress printing method, guravure printing method, and extrusion orcasting through a nozzle. In the case which the composition (x) isapplied in a small thickness, there can also be employed a method ofcoating the composition (x) containing a solvent and volatilizing thesolvent.

[0101] Except for the portion which should serve as a cut portion, theuncured coated composition (x) is irradiated with an active energy ray,thereby semi-curing the composition (x) at the irradiated portion andleaving the portion, that is not irradiated with the active energy ray,of the composition (x) as the uncured portion (hereinafter, thisoperation is occasionally referred to as “patterning exposure” or simplyas “exposure”). This step is referred to as the step (ii) of forming asemi-cured coating film. An irradiation angle is not specificallylimited and it is not necessary to irradiate in the directionperpendicular to the coating film surface.

[0102] As used herein, “semi-curing” means the curing degree which makesthe composition (x) non-flowable or slightly flowable, and also meanscuring to such an extent that unreacted active energy ray polymerizablefunctional groups can remain which can be polymerized by furtherirradiation with the active energy ray. The method of semi-curing thecomposition (x) is preferably a method of irradiating with an activeenergy ray at a dose which is insufficient to completely cure thecomposition (x), or a method of irradiating at a temperature lower thana reirradiation temperature described hereinafter, or a combination ofboth methods.

[0103] When the dose of the active energy ray is too small and thecuring degree is insufficient, it becomes impossible to form a cutportion having a desired shape because of insufficient selectivity uponremoval of the uncured portion. Also in the case in which the member (J)has a recessed portion on the surface in the step of bonding with themember (J), the composition (x) penetrates into the recessed portion,thereby causing clogging of the recessed portion and changing asectional area of the recessed portion. Therefore, it is not preferred.

[0104] When the dose of the active energy ray is too large and thecuring degree is excessive, the flexibility of the semi-cured coatingfilm is lost and the adhesion is lowered, thus causing insufficientbonding with the member (J). Preferred semi-curing degree can beappropriately determined by a simple test in the system to be used.

[0105] The shape of a pattern in the patterning exposure, that is, theshape, which serves as the cut portion, can be optionally determinedaccording to the purposes. Examples thereof include a portion of acommunicating passage, outlet, liquid storage chamber, reaction chamber,liquid-liquid contact portion, developing passage of chromatography orelectrophoresis, detection portion, or valve structure; space used asperipheral portion of a stopper, pressure tank, vacuum tank, or pressuredetection portion; and all or a portion of a cavity-shaped cut portionemployed as the space which is employed as a portion in which a sensoris embedded.

[0106] In the case in which the shape, which serves as the cut portion,is a linear shape in the face of the coating film, it may be in the formof a line, zigzag, swirl, or horseshoe. When used as a liquid storagechamber or a reaction chamber, it may be of a circular or rectangularshape. The shape, which serves as the cut portion, may be a microthroughhole which communicates the surface and the back surface of the coatingfilm. The cut portion may communicate or not communicate with theperipheral portion of the coating film, that is, peripheral portion ofthe microdevice.

[0107] In the case in which the cut portion has a linear shape view fromthe coating film surface, the cut portion, that is, the uncured portionhas a width within a range from 1 to 1000 μm. The width is preferably 1μm or more, more preferably 5 μm or more, and still more preferably 10μm or more. It becomes impossible to manufacture a microdevice havingthe uncured portion having a narrower width. The width of the uncuredportion is preferably 1000 μm or less, more preferably 500 μm or less,and still more preferably 200 μm or less.

[0108] When the width of the uncured portion is above the above range,the effects of the present invention are adversely affected. A ratio ofthe width to the depth of the groove is not specifically limited, but ispreferably within a range from 0.2 to 10, and more preferably from 0.5to 5. The size of the uncured portion formed by the exposure is notalways the same as that of the portion, which is not irradiated with theactive energy ray, and the size may be larger or smaller than that ofthe portion which is not irradiated with the active energy ray.

[0109] The size can vary depending on the kind and dose of the activeenergy ray, the reactivity of the compound (a), the kind and amount ofthe active energy ray polymerization initiator, and the amount of thepolymerization inhibitor and the delaying agent. However, the size doesnot change too much and changes about ½ to 2 times at most. Thesectional shape of the uncured portion may be in any form such asrectangle (including chamfered rectangle), trapezoid (includingchamfered trapezoid) or semicircle.

[0110] Examples of the active energy ray, which can be used in thepresent invention, include light rays such as ultraviolet light, visiblelight, infrared ray, laser beam and synchrotron radiation;electromagnetic radiation such as X-rays, gamma-rays and synchrotronradiation; and particle beams such as electron beams, ion beams,beta-rays and heavy particle beams. Among these active energy rays,ultraviolet light and visible light are preferred and ultraviolet lightis particularly preferred in view of handling properties and curingrate. For the purpose of increasing the curing rate and performingcomplete curing, the irradiation with the active energy ray ispreferably performed in a low oxygen concentration atmosphere. The lowoxygen concentration atmosphere is preferably nitrogen gas flow, carbondioxide gas flow, argon gas flow, vacuum or reduced-pressure atmosphere.

[0111] The method of irradiating the portion other than the portion,which serves as the cut portion, is not specifically limited and, forexample, there can be employed a photolithographic technique ofirradiating while masking the portion, which requires no irradiation, orscanning beam of the active energy ray such as laser beam.

[0112] In the method of the present invention, after the completion ofthe exposure, the uncured composition (x) of the non-irradiated portionis removed to form a resin cut portion (hereinafter, this operation isoccasionally referred to as “development”) . This step is referred to asthe “step (iii)”. The method of removing the uncured composition (x) isnot specifically limited and, for example, there can be employed methodssuch as blowing by compressed air, absorption by a filter paper, washingout by liquid flow of a non-solvent such as water, washing with asolvent, volatilization and decomposition.

[0113] Among these methods, washing out by liquid flow of thenon-solvent or washing with the solvent is preferred. The uncuredportion of the composition (x) is converted into a cut portion by thedevelopment. The shape and size of the cut portion thus formed aregenerally the same as those of the uncured portion of the composition(x), but do not completely correspond. For example, in the case ofblowing by compressed air or washing out by liquid flow of thenon-solvent, the width of the cut portion tends to be reduced ascompared with washing with the solvent. Also, the uncured composition(x) of the non-irradiated portion is not completely removed and theresulting cut portion has a round bottom and the bottom of the cutportion is not contacted with the coating substrate surface, sometimes.

[0114] In the case of forming the portion, which is not bonded but iscontacted with the member (J), at a portion of the resin layer (X) ofthe microdevice manufactured by the present invention, between the step(i) and the step (ii) and/or between the step (ii) and the step (iii)and/or between the step (iii) and the step (iv), a portion of thecoating film, which serves as the resin layer (X), is selectivelyirradiated with an active energy ray, thereby partially curing the resinlayer so that the irradiated portion is not bonded with another memberin the case of laminating with the another member in the step (iv). Thisstep is referred to as the “step (ii′)”.

[0115] In the case in which the step (ii′) is performed between the step(i) and the step (ii), the uncured coating film, which serves as theresin layer (X), is partially cured, and the portion, which serves asthe cut portion, is removed, followed by semi-curing. In the case inwhich it is performed between the step (ii) and the step (iii), thecoating film, which serves as the resin layer (X), is partially cured inthe state where the uncured portion and the semi-cured portion exist,and then the cut portion is formed.

[0116] In the case in which it is performed between the step (iii) andthe step (iv), a portion of the semi-cured coating film having the cutportion formed therein is partially cured. The step (ii′) and the steps(i), (ii) and (iii) may be performed at substantially the same time, ormay be performed in plural stages. The active energy ray used in thestep (ii′) is the same as that used in the step (ii) of semi-curing thecoating film.

[0117] This can also be applied to the case of forming the structurethat a portion of the resin layer (X) is not bonded but is contactedwith the member (K). In the case of forming the portion wherein aportion of the resin layer (X) is contacted with neither the member (J)nor the member (K), the same method can be employed.

[0118] In the case of forming the portion, which is not bonded with themember (K) but is bonded with the member (J), at a portion of the resinlayer (X), the portion can be formed in the same manner as describedabove, except that the step of partial curing is performed between thestep (iv) and the step (v), between the step (iv) and the step (vi),between the step (v) and the step (vi), between the step (vi) and thestep of laminating the member (K), or between the step (v) and the stepof laminating the member (K).

[0119] After the step (iii), the semi-cured coating film of thecomposition (x) is laminated with the member (J), thereby converting thesemi-cured coating film into a resin layer (X). This step is referred toas the “step (iv)”. Lamination of the semi-cured coating film of thecomposition (x) with the member (J) may be in the form according to theapplications and purposes and may not be performed over the entiresurface.

[0120] The shape of the member (J) is not specifically limited and canbe any shape according to the applications and purposes. For example,the member can be in the form of a sheet (including film and ribbon),plate, coating film, bar, tube, or molded article having a complicatedshape. In view of ease of molding and ease of lamination and bonding ofthe composition (x) and the semi-cured coating film, the surface to bebonded is preferably in the form of a plane or secondary curved surface,and particularly preferably a sheet or a plate. The member (J′)described hereinafter has a specific shape in the member (J).

[0121] The material of the member (J) is not specifically limited aslong as it can be bonded with the composition (x). Examples of thematerial, which can be used as the member (J), include polymer, glass,crystal such as quartz, ceramic, semiconductor such as silicon, andmetal. Among these materials, a polymer is particularly preferred inview of the ease of molding, high productivity, and low cost.

[0122] The member (J) may be formed on a substrate. The material of thesubstrate is not specifically limited, and may be, for example, polymer,glass, ceramic, metal or semiconductor. Also, the shape of the substrateis not specifically limited and may be, for example, a plate-shapedarticle, sheet-shaped article, coating film, bar-shaped article, paper,cloth, nonwoven fabric, porous material, or injection-molded article.The substrate may be integrated with this microdevice, or may be removedafter formation. Plural microdevices can be formed on one member (J),and, after the manufacture, plural microdevices can be obtained bycutting.

[0123] The polymer used as the member (J) may be a homopolymer or acopolymer, or may be a thermoplastic polymer or a thermosetting polymer.In view of the productivity, the polymer used as the member (J) ispreferably a thermoplastic polymer or active energy ray curable polymer.

[0124] Examples of the polymer, which can be used as the member (J),include styrene polymers such as polystyrene, poly-α-methylstyrene,polystyrene/maleic acid copolymer and polystyrene/acrylonitrilecopolymer; polysulfone polymers such as polysulfone and polyethersulfone; (meth)acrylic polymers such as polymethyl methacrylate andpolyacrylonitrile; polymaleimide polymers; polycarbonate polymers suchas bisphenol A polycarbonate, bisphenol F polycarbonate and bisphenol Zpolycarbonate; polyolefin polymers such polyethylene, polypropylene andpoly-4-methylpentene-1; chlorine-containing polymers such as vinylchloride and vinylidene chloride; cellulose polymers such as celluloseacetate and methylcellulose; polyurethane polymers; polyamide polymers;polyimide polymers; polyether or polythioether polymers, such aspoly-2,6-dimethylphenylene oxide and polyphenylene sulfide; polyetherketone polymers such as polyether ether ketone; polyester polymers suchas polyethylene terephthalate and polyarylate; epoxy resins; urearesins; phenol resins; fluorine polymers such as polyethylenetetrafluoride and PFA (copolymer of ethylene tetrafluoride andperfluoroalkoxyethylene), and silicone polymers such aspolydimethylsiloxane; and cured articles of the active energy raycurable composition (x) used in the present invention.

[0125] Among these polymers, styrene polymers, (meth)acrylic polymers,polycarbonate polymers, polysulfone polymers and polyester polymers arepreferred in view of good adhesion. The member (J) is preferably made ofthe cured article of the active energy ray curable resin. The member (J)may be composed of a polymer blend or a polymer alloy, or may becomposed of a laminate or the other composite. The member (J) maycontain additives such as modifiers, colorants, fillers and reinforcers.

[0126] Examples of the modifier, which can be mixed with the member (J),include hydrophobizing agents (water repellents) such as silicone oil orfluorine-substituted hydrocarbon; hydrophilizing agents such aswater-soluble polymer, surfactant, inorganic powders (e.g. silica gel);and plasticizers such as dioctyl phthalate. Examples of the colorant,which can be mixed with the member (J), include any dyes or pigments,fluorescent dyes or pigments, and ultraviolet absorbers. Examples of thereinforcer, which can be mixed with the member (J), include inorganicpowders such as clay; and inorganic and organic fibers or fabrics.

[0127] In the case in which the member (J) is made of a material havingpoor adhesion such as polyolefin, fluorine polymer, polyphenylenesulfide or polyether ether ketone, the adhesion is preferably impartedor improved by a surface treatment of the surface of the member (J) tobe bonded or the use of a primer. It is preferred to use a member (J)obtained by applying an active energy ray curable composition to form acoating film and irradiating with an active energy ray to form asemi-cured coating layer in order to improve the adhesion with the resinlayer (X). In view of the adhesion, it is more preferred to use the sameactive energy ray curable composition as that in the resin layer (X) tobe bonded.

[0128] Upon use of the microdevice of the present invention, the surfaceof the member (J) is preferably hydrophilized for the purpose of thesuppressing adsorption of a solute such as protein onto the surface ofthe device, in addition to an improvement in adhesion.

[0129] The member (J) may be a member having a recessed portion such asgroove on the surface, a member having no recessed portion on thesurface, a composition (x) (semi)-cured resin layer having no cutportion in the layer, or a separation membrane, or a composite thereof.Alternatively, the member (J) can be removed after laminating the resinlayer (X) thereon. Furthermore, the member (J) can be a member wherein asingle resin layer (X), a laminated plural resin layers (X) or a resinlayer (X) is laminated on another member. The single resin layer (X) canbe formed by the same method of removing the coating substrate in thestep (v) of the present invention.

[0130] The resin layer (X) is transferred onto the member (J) byremoving the coating substrate from the resin layer (X) bonded with themember (J). This step is referred to as the “step (v)”. The removingmethod is not specifically limited and can be peeling, dissolution,decomposition, meltingl, or volatilization. In view of highproductivity, peeling is preferred. Also, dissolution is preferredbecause a flexible thin resin layer (X) can be formed without causingbreakage.

[0131] In the case in which the coating substrate is removed by peeling,the step (vi) described hereinafter is preferably provided before thestep (v). Alternatively, it is provided before and after the step. Theremoval by peeling is not specifically limited and may be peeling bystretching, peeling using a knife, peeling by liquid flow such as waterflow, peeling by air flow such as compressed air, or natural peeling bydipping in water. It is also preferred to change temperature conditionsor to remove in water so as to facilitate peeling.

[0132] The peeling is facilitated by selecting a combination of thematerial of the coating substrate and the composition (x) and selectinga composition wherein it exhibits the adhesion in the state of theuncured coating film and the semi-cured coating film and the bondingstrength is lowered after curing. The method of removing by peeling is apreferred method in the case in which the resin layer (X) hascomparatively high rigidity, that is, it has a tensile modulus within arange from 0.1 to 10 GPa.

[0133] In the case in which the coating substrate is removed bydissolution, the step (vi) described hereinafter may be provided beforeor after this step (v). As a matter of course, it may be provided beforeand after this step. The removal by dissolution can be performed byselecting a combination of the material of the coating substrate and thecomposition (x), using a solvent capable of selectively dissolving thecoating substrate. Examples of the solvent include water, acid, alkali,lower alcohol, ketone solvent, ester solvent, ether solvent, andhydrocarbon. Also, the dissolution method is not specifically limitedand, for example, there can be employed methods such as dipping in aliquid, shower, and washing with steam.

[0134] These methods do not require that the coating substrate becompletely dissolved. If a portion of the coating substrate is swollenand dissolved, and then the coating substrate is peeled from the resinlayer (X), the object of the present invention can be sufficientlyattained. Therefore, there is also included a method wherein a portionof the coating substrate is swollen and dissolved by strongly spraying asolvent, capable of dissolving the coating substrate, such as water, andthen the coating substrate is peeled from the resin layer (X).

[0135] Among these methods, the method of dissolving with water, acid oralkali is preferred. The removal by dissolution is preferred in the casein which the step (vi) described hereinafter is provided before thisstep (v) and the removal is hardly performed by peeling like the casewhere the cut portion of the resin layer (X) is in the form ofcontinuous line, curve, or numerous lines. The method of removing bydissolution is a preferred method in the case in which the cured resinlayer (X) has relatively low rigidity, that is, it has a tensile moduluswithin a range from 1 to 700 MPa. The removal by dissolution isperformed by any method such as oxidative decomposition or hydrolysis,and can be handled in the same manner as in the case of the removal bydissolution.

[0136] Before and/after the step (v), that is, in the state where thecoating substrate is laminated and/or removed, the semi-cured resinlayer (X) was irradiated again with an active energy ray, therebyfurther curing the composition (x) and bonding with the member (J). Thisstep is referred to the “step (vi)”. The irradiation with the activeenergy ray in this step means that the composition (x) layer is cured tosuch an extent as to impart a sufficient strength to the microdevicemanufactured and to bond the cured article layer of the composition (x)with the member (J) at a sufficient strength.

[0137] In the case of the removal of the coating substrate in the step(v) is performed by peeling, it means curing to such an extent as topeel. Therefore, it is not necessary to cure until polymerizable groupscompletely disappear. In particular, in the case in which another memberis laminated and bonded with the resin layer (X), the curing ispreferably performed to such an extent that polymerizable groups remain,thereby bonding with the another member after a third irradiation withthe active energy ray, while curing to such an extent as to peel thecoating substrate.

[0138] As the active energy ray, which can be used to cure in the step(vi), there can be used those listed as active energy rays which can beused to semi-cure the composition (x). The active energy ray used inthis step may be the same as or different from that used in the step(ii). Also, the irradiation conditions such as intensity, irradiationtemperature, and atmospheric oxygen concentration may vary.

[0139] The resin layer (X) has a resin cut portion formed by patterningexposure and development therein, and the cut portion can constitute acavity used as the passage by laminating the layer with the member (J)and optionally laminating another member (K) on the resin layer (X),thereby interposing the resin layer (X) between the member (J) and theanother member (K). The cavity may communicate or not communicate withthe exterior of the microdevice. The resin layer (X′) describedhereinafter has a specific shape in the resin layer (X).

[0140] After laminating the resin layer (X) on the member (J), pluralresin layers (X) can be laminated by using the member (J) laminated withthe resin layer (X) in place of the member (J) in the step (iv) andrepeating the step of forming the resin layer (X), that is, a series ofthe steps (i), (ii), (iii), (iv) and (v), or a series of the steps (i),(ii), (iii), (iv), (v) and (vi), or a series of the steps (i), (ii),(iii), (iv), (vi) and (v).

[0141] At this time, it is not necessary to perform the step (vi), butis sometimes required to perform this step according to the method ofpeeling the substrate. The shape of the resin layer (X) of continuoustwo resin layers (X) may be the same or different, and the thickness andthe kind of the composition (x) constituting the layer (X) may bedifferent. In the case of repeating twice or more, a series of the stepsselected from the above steps can be performed.

[0142] In the method of the present invention, preferred procedurevaries depending on the method of removing the coating substrate in thestep (v). For example, in the case in which the coating substrate isremoved by dissolution, the semi-cured resin layer (X) is laminated withanother member (K), thereby interposing the resin layer (X) between themember (J) and the another member (K), and then the irradiation withactive energy ray in the step (vi) is performed in this state, therebybonding them, preferably.

[0143] In the case in which the coating substrate is removed bydissolution, plural resin layers (X) are laminated by using the resinlayer (X) in a semi-cured state after removing the coating substrate inplace of the member (J) and repeating a series of any steps describedabove, and then the irradiation with active energy ray in the step (vi)is performed in this state, thereby bonding them.

[0144] In the case in which the coating substrate is removed by peeling,it is made possible to manufacture a microdevice, wherein the resinlayer (X) is laminated with plural layers, by performing the step (vi)before the step (v), using the cured resin layer (X) formed on themember (J) after removing the coating substrate in place of the member(J) and repeating the steps (i), (ii), (iii), (iv), (vi) and (v).

[0145] It is made possible to manufacture a microdevice having pluralresin layers (X) by laminating another resin layer (X) on the resinlayer (X) via another member in the same manner as described above, orforming a member wherein the resin layer (X) is formed on the member (J)and laminating plural members.

[0146] Connection of the cut portions of continuous three or moremembers enables cavity-shaped passages to intersect three-dimensionallyand also enables the microdevice to be provided with a complicatedfunction. Such a form can be a member (J)-resin layer (X)-member (K)laminate using a member (J) selected from a member having a cut portionpiercing through the member, a member having a recessed cut portion onthe surface and a member having a cut portion piercing through themember and a recessed cut portion on the surface, and a member (K)having the same structure as that of the member (J). At this time, themember (K) is made of the same material as that of the resin layer (X)and has the same structure as that of the resin layer (X), and the resinlayer (X) may be plural layers, and also the member (J) is made of thesame material as that of the resin layer (X) and has the same structureas that of the resin layer (X).

[0147] It is also preferred to closely contact the another member (K)with the surface of the resin layer (X) thus formed. The close adhesioncan be bonding, adhesion or non-bonded close adhesion, but is preferablybonding. The bonding method is not specifically limited, but ispreferably a method of using an active energy ray curable composition asthe material of the member (K), bringing the composition into contactwith the resin layer (X) in a semi-cured state, and irradiating againwith an active energy ray thereby bonding them. It is also preferred toform in the same manner as in the case of the resin layer (X), exceptthat no cut portion is formed. The member (K′) described hereinafter hasa specific shape of the member (K).

[0148] The shape and the size of the member (K) are the same as those ofthe member (J). The member (K) can be a member having a cut portionpiercing through the member, a member having a recessed cut portion suchas groove on the surface, a member having neither a cut portion piercingthrough the member nor a recessed cut portion on the surface, a resinlayer, which is made of the same material as that of the resin layer (X)and has the same structure as that of the resin layer (X), formed by thesame manner as in the case of the resin layer (X), a (semi)-cured resinlayer of a composition (x) having no cut portion in the layer, or aseparation membrane, or a composite thereof. The member wherein theresin layer (X) is laminated on any member can be used in place of themember (K).

[0149] The hardness of the resin layer (X) can be controlled to thedesired hardness by selecting the radiation polymerizable compound (a)and the respective components of the composition (x). The tensileelasticity of the resin layer (X) can be controlled within a range from0.01 to 10 GPa, and preferably from 0.05 to 3 GPa.

[0150] The microdevice of the present invention can be replaced by amicrodevice having a valve by providing the resin layer (X) with astructure which serves as a stopper. The structure, which serves as thestopper, is preferably in the form of a sheet, a portion of which isfixed, in view of ease of the manufacture. The sheet, a portion of whichis fixed, can be a tongue, circle or rectangle, which is fixed at one ormore portions.

[0151] According to the method of the present invention, it is madepossible to form a sheet-shaped stopper, a portion of which is fixed, bysubjecting the peripheral portion of the portion, which serves as thestopper, to exposure in the shape, which serves as the cut portion, inthe step (ii) of the present invention. In order to form a structure,which serves as a tongue-shaped stopper, the exposure is performed so asto form a horseshoe-shaped cut portion.

[0152] Then, a valve can be formed by laminating a member (J), a member(K) or a resin layer (X), having an orifice-shaped cut portion having asmaller area than that of the stopper, on one side of the resin layer(X) having the stoppre formed thereon while aligning the orifice-shapedcut portion with the stopper, and laminating a member (J), a member (K)or a resin layer (X), having a cut portion, which serves as a cavitylarger than the stopper, on the other side of the resin layer (X) sothat the stopper can move.

[0153] In the case of bonding the resin layer (X) with another member orthe resin layer, for example, the member (J), the member (K) or theresin layer (X), having an orifice-shaped cut portion having a smallerarea than that of the stopper, the portion, which serves as the stopperof the resin layer (X), is preferably irradiated with an active energyray, thereby accelerating curing without bonding of the portion beforethe step (iv) in order to avoid bonding of the stopper portion. Theirradiation with the active energy ray is preferably performed on thestep (ii) and/or between the step (iii) and the step (iv).

[0154] The resin layer (X) to be provided with the stopper is preferablyformed of a flexible material and is preferably formed of a materialhaving a lower tensile elasticity than that of the layers or members,between which the layer is interposed. The tensile elasticity of thematerial used in the resin layer (X) to be provided with the stopper ispreferably within a range from 1 MPa to 1 GPa, more preferably from 10to 500 MPa, and still more preferably from 50 to 300 MPa. When thetensile elasticity is less than the above range, the resulting resinlayer is likely to be inferior in strength and repeating durability. Onthe other hand, when the tensile elasticity is more than the aboverange, leakage is likely to occur upon closure.

[0155] According to the manufacturing method of the present invention,in the case of manufacturing a microdevice having a movable diaphragmsimilar to the case of manufacturing a microdevice having a stopper, itis preferred to provide the step of irradiating the portion, whichshould not be bonded with the resin layer (X), with an active energyray, thereby accelerating curing without bonding the portion between thestep (i) and the step (iv) when the resin layer (X) is adjacent to thediaphragm in order to prevent bonding of the diaphragm with adjacentmember, that is, the resin layer (X), the member (J) or the member (K).

[0156] Examples of the microdevice, which can be manufactured by such amethod, include microdevices having a diaphragm valve mechanism, a checkvalve mechanism, a diaphragm type on-off valve mechanism or a diaphragmtype flow rate control valve mechanism.

[0157] The microdevice thus manufactured can also be subjected topostworking such as perforation or cutting. Since the microdevice of thepresent invention is small as a whole, simultaneous manufacture ofnumerous members in a single resin layer is useful for manufacturingefficiency and positioning of details of the respective members withgood accuracy. That is, numerous microdevices having high-accuracydimensional stability can be manufactured at a time with goodreproducibility by manufacturing plural microdevices on oneexposure/development plate.

[0158] The microdevice of the present invention is a microdevice havinga laminated structure comprising a member (J′) (selected from a memberhaving a cut portion piercing through the member, a member having arecessed cut portion on the surface, and a member having a cut portionpiercing through the member and a recessed cut portion on the surface},one or more active energy ray curable resin layers (X′) having a cutportion at a portion of the layer, the cut portion having a minimumwidth within a range from 1 to 1000 μm, and a member (K′) {selected froma member having a cut portion piercing through the member, a memberhaving a recessed cut portion on the surface, and a member having a cutportion piercing through the member and a recessed cut portion on thesurface}, which are laminated, while two or more cut portions in themembers are connected to form a cavity.

[0159] The member (J′) is the same as the member (J) used in the methodof the present invention, except that it is a member having a cutportion piercing through the member, a member having a recessed cutportion such as groove on the surface, or a member having a cut portionpiercing through the member and a recessed cut portion on the surface,and also has a specific shape of the member (J). Also, the member (K′)is the same as the member (K) used in the method of the presentinvention, except that it is a member having a cut portion piercingthrough the member, a member having a recessed cut portion such asgroove on the surface, or a member having a cut portion piercing throughthe member and a recessed cut portion on the surface, and also has aspecific shape of the member (K).

[0160] The position, the shape, and the size of the cut portion piercingthrough the member are not specifically limited as long as the cutportion is open to the face which can be connected with the resin layer(X′). The cut portion piercing through the member can be a cut portionhaving a complex shape such as circular orifice, rectangular orifice,slit, cone, pyramid, barrel, or threaded orifice. The cut portion of themember (J′) can be in the form of an orifice larger than that of theresin layer (X′) and the size and shape of the recessed cut portionformed on the member (J′) surface is the same as those of the cavityformed in the microdevice of the present invention describedhereinafter.

[0161] The method of manufacturing the member (j′) and the member (K′),which have the cut portion, is not specifically limited and they can bemanufactured, for example, by an injection molding method, a meltreplica method, a solution casting method, a photolithograph methodusing an active energy ray curable composition, or a cast molding methodusing an active energy ray curable composition. The member (J′) can be aresin layer, which is made of the same material as that of the resinlayer (X′) in the present invention and has the same shape as that ofthe resin layer (X′), and the resin layer (X′) in the present inventioncan be a multi-layered structure or a laminate wherein the resin layer(X′) in the present invention is laminated with another member.

[0162] The microdevice of the present invention is a laminate of amember (J′), one or more resin layers (X′) and a member (K′) and thetotal number of the layers is 3 or more, preferably within a range from3 to 10, and more preferably from 3 to 6, although this varies dependingon the applications and purposes.

[0163] In the microdevice of the present invention, unlike the resinlayer (X) in the method of the present invention, the cut portion formedon the resin layer (X′) pieces through the resin layer and the resinlayer is laminated with another resin layer (X′) or the member having athrough hole and a recessed portion to form a cavity which communicateswith these layers and the member. The resin layer (X′) is the same asthe resin layer (X) in the method of the present invention, except thatthe cut portion formed on the resin layer pierces through the resinlayer.

[0164] In the microdevice of the present invention, among the respectivecut portions formed in the member (J′), one or more resin layers (X′)and the member (K′), the cut portions of at least two adjacent layerscommunicate with each other to form a cavity. Preferably, the cutportions of continuous three or more layers communicate with each otherto form a cavity.

[0165] It is also possible to further laminate another member, forexample, a member having a cut portion with the microdevice of thepresent invention. Also, two or more microdevices of the presentinvention can be bonded so that cavities open to the surface arecommunicated with each other to manufacture a new microdevice.Alternatively, they can be laminated and bonded while interposing amember having neither a through hole nor recessed portion to manufacturea microdevice composed of plural portions wherein cavities are notcommunicated with each other.

[0166] Examples thereof include a microdevice having a diaphragmstructure such as diaphragm type pump mechanism or diaphragm valvemechanism, wherein a member having neither a through hole nor a recessedportion forms a diaphragm. The member having neither a through hole nora recessed portion is preferably formed of an active energy ray curableresin because of high interlaminar adhesion and high productivity. Sucha member can be a porous membrane, a dialysis membrane or a gasseparation membrane.

[0167] The shape of the cavity in the microdevice of the presentinvention can be optionally determined according to the applications andpurposes. Examples thereof include a portion of communicating passage,outlet, liquid storage chamber, reaction chamber, liquid-liquid contactportion, developing passage of chromatography or electrophoresis,detection portion, or valve structure; space used as peripheral portionof valve, pressure tank, vacuum tank, or pressure detection portion; andall or a portion of a cavity-shaped cut portion employed as the spacewhich is employed as a portion in which a sensor is embedded.

[0168] Preferably, plural passages or branched passages formed indifferent resin layers (x′) intersect three-dimensionally across theresin layer (X′) because a complicated device can be manufactured as aresult of release from such a restriction that passages must be formedin the plane.

[0169] In the present invention, the cavity can constitute a portion ofthe valve. The kind of valve is not specifically limited and examplesthereof include a check valve (valve which is normally closed and isopened when a predetermined or greater pressure is applied), non-returnvalve (valve which is normally open in a certain direction and is closedin the reverse direction), on-off valve, flow rate control valve and soon.

[0170] In the case the valve has a stopper, the shape of the stopper isnot specifically limited and can be in the form of sheet (includingfilm, membrane, ribbon and plate), a portion of which is fixed, such astongue; and independent bulk such as sphere, cone, and plate containedin the cavity. The structure, which serves as the stopper, is preferablyin the form of a sheet, a portion of which is fixed, because of ease ofmanufacture.

[0171] The sheet, a portion of which is fixed, can be a tongue, circle,or rectangle, which is fixed at one or more portions. According to themethod of the present invention, it is made possible to form asheet-shaped stopper, a portion of which is fixed, having the peripheralportion of the portion, which serves as the stopper, as a cut portion ata portion of the resin layer (X′).

[0172] A structure, which serves as a tongue-shaped stopper, can beobtained when the cut portion is in the form of a horseshoe. Anorifice-shaped cut portion having a smaller area than that of thestopper is laminated on one side of the resin layer (X′) having thestopper formed thereon while aligning the orifice-shaped cut portionwith the stopper, and a cavity larger than the stopper is formed on theother side of the resin layer so that the stopper can move, thus makingit possible to function as a valve.

[0173] The resin layer (X′) having the stopper is preferably formed of aflexible material and is preferably formed of a material having a lowertensile elasticity than that of the layers or members, between which theresin layer is interposed. The tensile elasticity of the material usedin the resin layer (X′) having the stopper is preferably within a rangefrom 1 MPa to 1 GPa, more preferably from 10 to 500 MPa, and still morepreferably from 50 to 300 MPa. When the tensile elasticity is less thanthe above range, the resulting resin layer is likely to be inferior instrength and repeating durability. On the other hand, when the tensileelasticity is more than the above range, leakage is likely to occur uponclosure.

[0174] Also, the present invention provides a microdevice having adiaphragm type valve mechanism. A preferred first embodiment of thediaphragm valve mechanism has a configuration such that the resin layer(X′) is directly laminated with a member, which serves as a diaphragm,at one surface and is directly laminated with another member having acut portion at the other surface, and the cut portions of the resinlayer (X′) form a cavity by lamination, while the another memberlaminated on the back surface of the resin layer (X′), which serves asthe diaphragm, has an orifice-shaped cut portions, which serve as aninlet and/or an outlet to the cavity, at least one of the inlet and theoutlet being formed across the resin layer (X′) from the diaphragm, andthe peripheral portion does not contact with the diaphragm and thepassage can be closed by deforming the diaphragm to contact with theperipheral portion of at least one of the inlet and the outlet.

[0175] In the case in which the orifice-shaped cut portion formed at apredetermined position of the another member is either an inlet or anoutlet, the other one can be a capillary passage composed of a linearcut portion formed on the resin layer (X′) and a resin layer, whichserves as a diaphragm, or a capillary passage composed of agroove-shaped cut portion formed on the another member and the resinlayer (X′).

[0176] Examples of the valve having such a structure include a diaphragmvalve which is normally open. The structure wherein the resin layer,which serves as a diaphragm, the resin layer (X′) and another member arebonded and laminated can be manufactured by the method of the presentinvention.

[0177] The present invention also provides a microdevice having alaminated structure wherein a member (J′) {selected from a member havinga cut portion piercing through the member, a member having a recessedcut portion on the surface, and a member having a cut portion piercingthrough the member and a recessed cut portion on the surface}, one ormore active energy ray curable resin layers (X′) having a cut portion ata portion of the layer, the cut portion having a minimum width within arange from 1 to 1000 μm, and a member (K″) having no cut portion, whichserves as a diaphragm, are laminated and the member (K″) has a portion,which is not bonded but is contacted with another member laminatedadjacent thereto, the portion being a diaphragm portion, while two ormore cut portions in the member (J′) and the resin layer (X′) areconnected to form a cavity.

[0178] That is, the present invention provides a microdevice comprisinga laminate of a member (J′), one or more resin layers (X′) and a member(K″) having no cut portion, wherein the member (K″) has a portion, whichis not bonded but is contacted with another member laminated adjacentthereto and the portion is a diaphragm portion.

[0179] The member (J′) and the resin layer (X′) are the same as themember (J′) and the resin layer (X′) described above, and themicrodevice is the same as the microdevice comprising the member (J′),the resin layer (X′) and the member (K′), except that the member (K″)having no cut portion, which serves as the diaphragm, is used in placeof the member (K′).

[0180] The member (K″) has a portion, which is not bonded but iscontacted with another member laminated with the member, and the portionserves as the diaphragm portion. That is, when the diaphragm isdeformed, the non-bonded portion can be converted into a cavity.

[0181] A preferred second embodiment of the diaphragm valve mechanism ofthe present invention is characterized in that it has the abovestructure and, moreover, the resin layer (X′) has orifice-shaped cutportions, which serve as an inlet and/or an outlet, to the portion whichcan form the cavity, at least one of the inlet and the outlet beingformed across the member from the diaphragm, and the peripheral portiondoes not contact with the diaphragm and the passage can be opened bydeforming the diaphragm to contact with the peripheral portion of atleast one of the inlet and the outlet.

[0182] In the case in which the orifice-shaped cut portion formed at apredetermined position of the resin layer (X′) is either an inlet or anoutlet, the other one can be formed as a connection port to the portion,which forms a cavity, of a passage composed of a linear cut portion ofthe resin layer (X′) and a diaphragm.

[0183] The member (J′) can be provided with a cut portion, which servesas a passage connected to an inlet and/or an outlet. The structurewherein the member (J′), the resin layer (X′) and the member (K″) arebonded and laminated can be manufactured by the method of the presentinvention. Examples of the valve having such a structure includediaphragm valve and check valve which are normally closed.

[0184] In the above first and second embodiments, the thickness of thediaphragm is preferably within a range from 1 to 500 μm, and morepreferably from 5 to 200 μm. An optimum value of the thickness of thediaphragm varies depending on the size of the cavity portion. As thearea of the cavity becomes smaller, the thickness is preferably reduced.However, when the thickness is less than the above range, it becomesdifficult to manufacture the diaphragm. On the other hand, when thethickness exceeds the above range, merits as a microdevice are reduced.

[0185] The diaphragm is preferably formed of a material having a tensileelasticity within a range from 1 to 700 MPa, and more preferably from 10to 300 MPa. Although it varies depending on the diameter of thediaphragm and the hardness of the material, when the tensile elasticityis less than the above range, it becomes difficult to manufacture thediaphragm. On the other hand, when the tensile elasticity exceeds theabove range, it becomes difficult to perform opening and closing.

[0186] The material constituting the diaphragm preferably has a breakingelongation as measured by the method defined in Japanese IndustrialStandard (JIS) K-7127 of 2% or more, and more preferably 5% or more.Although there is not an upper limit of the breaking elongation, as amatter of course, it is not necessary to set the upper limit becausehigh breaking elongation does not exert an adverse influence and, forexample, the breaking elongation may be 400%. In the present invention,even when using a material, which exhibits a low breaking elongationwithin a range from 2 to 5% in a tensile test in accordance with JISK-7127, it is less likely to be broken in the operation of the method ofthe present invention. The material can be used without being brokeneven if strain of more than the breaking elongation in the above test isapplied.

[0187] The method of deforming the diaphragm may be any method andexamples thereof include pressure injection of fluid into a cavityformed on the opposite side of the diaphragm, change in pressure such asreduced pressure, mechanical compression or suction and the like.

[0188] The present invention can provide a microdevice having amulti-layered structure comprising plural layers, particularly three ormore layers having a cavity, a portion of which is used as a passage.Also, the present invention can provide a microdevice having a valvestructure, which is capable of easily forming a fine stopper and a thinflexible diaphragm and bonding them to the desired position.Furthermore, it is made possible to obtain a device which causes neitherclogging of a passage due to an adhesive nor leakage of liquid from thespace between the respective layers or the space between the layer andanother member. Furthermore, a chemical device, which causes neitheradsorption nor loss of a biological component and exhibits excellentreproducibility, can be obtained by using an amphipathic polymerizablecompound. Consequently, it is made possible to provide a microdevicewhich can perform complicated reaction and analysis processes.

EXAMPLES

[0189] The present invention will now be described in detail by way ofExamples and Comparative Examples, but the present invention is notlimited to these Examples. In the following Examples, “parts” and“percentages” are by weight unless otherwise specified.

[0190] Irradiation with Active Energy Ray

[0191] Using a light source unit for exposure apparatus, ModelMulti-Light 200, manufactured by USHIO INC. comprising a 200 W metalhalide lamp as a light source, irradiation with ultraviolet light havingan ultraviolet intensity of 100 mW/cm² at 365 nm was performed in anitrogen atmosphere at room temperature.

[0192] Preparation of Composition (x)

[0193] Preparation of Composition (x-1)

[0194] 30 Parts of a trifunctional urethane acrylate oligomer (“UNIDICV-4263”, manufactured by Dainippon Ink and Chemicals, Inc.) having anaverage molecular weight of about 2000 and 45 parts of 1,6-hexanedioldiacrylate (“KAYARAD HDDA”, manufactured by Nippon Kayaku Co., Ltd. as aradiation polymerizable compound (a), 25 parts of nonylphenoxypolyethylene glycol (n=17) acrylate (“N-177E”, manufactured by DAI-ICHIKOGYO SEIYAKU CO., LTD.) as an amphipathic compound (b), 5 parts of1-hydroxycyclohexyl phenyl ketone (“IRGACURE 184”, manufactured by CibaGeigy Co.) as a photopolymerization initiator and 0.1 parts of2,4-diphenyl-4-methyl-1-pentene (manufactured by KANTO KAGAKU CO., LTD.)as a polymerization-delaying agent were mixed to prepare an activeenergy ray curable composition (x-1). An ultraviolet cured article ofthe active energy ray curable composition (x-1) had a tensile elasticityof 560 MPa and a contact angle with water of 12 degrees.

[0195] Preparation of Composition (x-1′)

[0196] A composition (x-1′) having the same composition as that of thecomposition (x-1) was prepared, except that it contains 2 parts of thephotopolymerization initiator and does not contain thepolymerization-delaying agent. An ultraviolet cured article of theactive energy ray curable composition (x-1′) had a tensile elasticity of580 MPa and a contact angle with water of 12 degrees.

[0197] Preparation of Composition (x-2)

[0198] 75 Parts of a polytetramethylene glycol (average molecularweight: 250) maleimide capriate (synthesized by the method described inSynthesis Example 13 of Japanese Unexamined Patent Application, FirstPublication (Kokai) No. 11-124403) as a radiation polymerizable compound(a), 25 parts of nonylphenoxy polyethylene glycol (n=17) acrylate(“N-177E”, manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.) as anamphipathic compound (b) and 0.01 parts of2,4-diphenyl-4-methyl-1-pentene (manufactured by KANTO KAGAKU CO., LTD.)as a polymerization-delaying agent were mixed to prepare an activeenergy ray curable composition (x-2) . An ultraviolet cured article ofthe active energy ray curable composition (x-2) had a tensile elasticityof 610 MPa and a contact angle with water of 19 degrees.

[0199] Preparation of Composition (x-2′)

[0200] A composition (x-2′) having the same composition as that of thecomposition (x-2) was prepared, except that it did not contain thepolymerization-delaying agent. An ultraviolet cured article of theactive energy ray curable composition (x-2′) had a tensile elasticity of630 MPa and a contact angle with water of 19 degrees.

[0201] Preparation of Composition (x-3)

[0202] 30 Parts of a trifunctional urethane acrylate oligomer (“UNIDICV-4263”, manufactured by Dainippon Ink and Chemicals, Inc.) having anaverage molecular weight of about 2000, 45 parts of an alkyl diacrylate(“SARTOMER C2000”, manufactured by SOMAR CORP.) containingω-tetradecanediol diacrylate and ω-pentadecanediol diacrylate as a maincomponent and 25 parts of a nonylphenoxy polyethylene glycol (n=17)acrylate (“N177E”, manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD. as aradiation polymerizable compound (a), 5 parts of 1-hydroxycyclohexylphenyl ketone (“IRGACURE 184”, manufactured by Ciba Geigy Co.) as aphotopolymerization initiator and 0.1 parts of2,4-diphenyl-4-methyl-1-pentene (manufactured by KANTO KAGAKU CO., LTD.)as a polymerization-delaying agent were mixed to prepare an activeenergy ray curable composition (x-3). An ultraviolet cured article ofthe active energy ray curable composition (x-3) had a tensile elasticityof 160 MPa and a contact angle with water of 14 degrees.

Example 1

[0203] In this Example, a method of producing a microdevice of thepresent invention using an acrylic resin as the composition (x) by amethod of peeling a coating substrate will be described.

[0204] Step (i)

[0205] As a coating substrate (1), a 30 μm thick biaxially stretchedpolypropylene film (OPP film, manufactured by Futamura ChemicalIndustries Co., Ltd.), one surface of which is subjected to a coronadischarge treatment was used after cutting into a size of 5 cm×5 cm. Onthe surface subjected to the corona treatment, the composition (x-1) wasapplied using a 127 μm thick bar coater to form a coating film (2).

[0206] Step (ii)

[0207] In a nitrogen atmosphere, a portion other than a non-exposureportion (3) shown in FIG. 1 was irradiated with ultraviolet light via aphotomask having a width of a non-exposure portion of 100 μm and alength of a non-exposure portion of 30 mm for one second, therebysemi-curing the portion.

[0208] Step (iii)

[0209] While exposing the semi-cured coating film to running water froma tap, the uncured composition (x-1) at the non-exposure portion (3) waswashed and removed to form a semi-cured coating film (2) having a cutportion (3) on the coating substrate (1).

[0210] Manufacture of Member (J-1)

[0211] In the same manner as in the case of forming the semi-curedcoating film (2), except that a plate-shaped base material (4) havingdimensions of 5 cm×5 cm×3 mm (thickness) made of polystyrene(“DICSTYRENE XC-520”, manufactured by Dainippon Ink and Chemicals, Inc.)was used in place of the coating substrate (1) and a composition (x-1′)was used in place of the composition (x-1) and, furthermore, thephotomask was not used during the exposure, a member (J-1), wherein asemi-cured coating film (5) made of the composition (x-1′) is formed onthe surface of the base material (4), was manufactured.

[0212] Step (iv)

[0213] On the surface of the member (J-1) on which the semi-curedcoating film (5) was formed, the semi-cured coating film (2) formed onthe coating substrate (1) was laminated to obtain a resin layer (X-1)precursor (2′) in a semi-cured state.

[0214] Step (vi)

[0215] The resulting laminate was irradiated with the same ultravioletlight as that used in the exposure without using the photomask for 5minutes, thereby further curing the resin layer (X-1) precursor (2′) toform a resin layer (X-1) (2′) and bonding with the resin layer (5) ofthe member (J-1).

[0216] Step (v)

[0217] Then, the coating substrate (1) was peeled off from thefour-layered laminate to manufacture a microdevice (D-1) wherein theresin layer (X-1) (2′), that is, a layer of a cured article made of thecomposition (x-1), which has the cut portion (3), is bonded on the resinlayer (5) of the member (J-1).

[0218] Bonding of Member (K-1)

[0219] In the same manner as in the case of the member (J-1), exceptthat a plate having dimensions of 5 cm×5 cm×3 mm (thickness) made ofpolystyrene((“DICSTYRENE XC-520”, manufactured by Dainippon Ink andChemicals, Inc.) was used as a member (K-1) (6) in place of the basematerial, a semi-cured coating film (7) made of the composition (x-1′)was formed as a bonding resin layer on the member (K-1) (6) and thenclosely contacted with the surface of the resin layer (X-1) (2′).

[0220] Step (vi)

[0221] While maintaining the state, irradiation with the sameultraviolet light as that used in the exposure was performed withoutusing the photomask for 30 seconds, thereby curing the semi-curedcoating film (7) to form a resin layer (7) and bonding the member (K-1)(6) and the resin layer (7) with the surface of the resin layer (X-1)(2) to turn the cut portion (3) of the resin layer (X-1) (2) into cavity(3′), and thus entire active energy ray curable composition (x) wascompletely cured.

[0222] Formation of Other Structures

[0223] At both ends of the capillary cavity (3′), an orifice having adiameter of 1.6 mm was made in the member (K-1) (6) and the adhesiveresin layer (7) using a drill and a stainless steel pipe having adiameter of 1.6 mm was bonded using an epoxy resin to form an inlet (8)and an outlet (9), thereby manufacturing a microdevice (D-1) having thecapillary cavity (3′) therein as shown in FIG. 2 and FIG. 3.

[0224] Leakage Test

[0225] Water was poured through the inlet (8) of the microdevice (D-1)and, after closing the outlet (9), the microdevice was allowed to standfor one hour in a state where a pressure of 0.1 MPa is applied in thecavity. As a result, leakage of water was not recognized.

[0226] Observation of Cavity Portion

[0227] The microdevice (D-1) was cut and observed by a scanning electronmicroscope (SEM). As a result, the capillary cavity (3′) had arectangular cross section of 95 μm in width and 60 μm in height.

Example 2

[0228] In this Example, the method of the present invention using amember (J) having a recessed cut portion on the surface will bedescribed.

[0229] Manufacture of Member (J)

[0230] A member (J-2) was manufactured by interposing a plate havingdimensions of 5 cm×5 cm×3 mm (thickness) made of polystyrene(“DICSTYRENE XC-520”, manufactured by Dainippon Ink and Chemicals, Inc.)and a mold made of a silicon wafer between glass plates, fastening themwith a spring clamp, heating in a hot-air oven at 120° C. for about 2hours, cooling to room temperature, removing the mold and the glassplates to form a groove-shaped recessed portion having the same shapeand length as those in Example 1, except that a groove has a width of 50μm and a depth of 25 μm, on the surface of a polystyrene plate.

[0231] Formation of Semi-Cured Coating Film

[0232] In the same manner as in Example 1, except that a pattern ofexposure has a configuration such that each orifice having a diameter of300 μm is formed at the position corresponding to both ends of thegroove formed on the member (J-2), a semi-cured coating film having twoorifice-shaped cut portions on a coating substrate (steps (i), (ii) and(iii)).

[0233] Formation of Resin Layer (X-2)

[0234] The semi-cured coating film formed on the coating substrate wascontacted with the groove-formed surface of the member (J′-2) whilealigning them (step (iv)) and the semi-cured coating film was cured byirradiating with the same ultraviolet light as that used in the exposurewithout using a photomask for 30 seconds to form a resin layer (X-2)(the step (vi)). Then, the coating substrate was peeled off from thethree-layered laminate (step (v)) to manufacture a microdevice (D-2)including a cavity having the same shape as that of the cavities in FIG.2 and FIG. 3, wherein the resin layer (X-2), that is, a layer of a curedarticle made of the composition (x-1), which has the cut portion, thatserves as an inlet and outlet, is bonded on the surface of the member(J-2).

Example 3

[0235] In this Example, a method of producing a microdevice of thepresent invention using a maleimide resin as the composition (x) by amethod of peeling a coating substrate will be described. In the samemanner as in Example 1, except that a composition (x-2) was used as thecomposition (x) in place of the composition (x-1) and a composition(x-2′) was used in place of the composition (x-1′) and, furthermore, theexposure time was 2 seconds, a microdevice (D-3) having the samestructure as that in Example 1 was manufactured.

Example 4

[0236] In this Example, a microdevice comprising laminated three resinlayers (X′) having passages, which intersect three-dimensionally,therein, and a method of manufacturing the same, will be described.

[0237] Manufacture of Member (J-4-1)

[0238] In the very same manner as in Example 1, a member (J-4-1) whereina semi-cured composition (x-1′) resin layer (36) having no cut portionis formed on the surface of a base material (35) was manufactured.

[0239] Formation of Resin Layer (X′-4-1)

[0240] In the same manner as in Example 1, except that the non-exposureportion comprises a non-exposure portion (33) having a width of 100 μmand a length of 30 mm and a non-exposure portion (34) wherein twostraight lines having a width of 100 μm and a length of 14 mm arelinearly arranged at a interval of 2 mm in a direction perpendicular tothe non-exposure portion (33), as shown in FIG. 4, a semi-cured coatingfilm (32) having the cut portions (33) and (34) of a coating film wasformed on a coating substrate (31) and, after laminating on the surfaceof a member (J-4-1) (35), a resin layer (X′-4-1) (32′) having cutportions (33′) and (34′) was formed by irradiating with ultravioletlight for 10 seconds to manufacture a member (J′-4-2).

[0241] Formation of Resin Layer (X′-4-2)

[0242] In the same manner as in the case of the formation of the resinlayer (X′-4-1), except that the member (J′-4-2) was used in place of themember (J-4-1) and a non-exposure portion (38) comprises two circularportions formed at an interval of 2 mm, each having a diameter of 300μm, which serve as a cut portion (38′) serving as an interlaminarcommunicating passage, as shown in FIG. 8, a semi-cured coating film(37) having the cut portion (38) of a coating film was transferred ontothe resin layer (X′-4-1) to form a resin layer (X′-4-2) (37′) having thecut portion (38′), thereby manufacturing member (J′-4-3).

[0243] Formation of Resin Layer (X′-4-3)

[0244] In the same manner as in the case of the formation of the resinlayer (X′-4-1), except that the member (J′-4-3) was used in place of themember (J-4-1) and a non-exposure portion (40) has a linear shape havinga width of 100 μm and a length of 2 mm, which serves as a cut portion(40′) for communicating two cut portions (34′) in FIG. 8 via aninterlaminar communicating passage (38′), a semi-cured coating film (39)having the cut portion (40) of a coating film onto the resin layer(X′-4-2) to form a resin layer (X′-4-3) having the cut portion (40′).

[0245] Bonding of Member (K-4)

[0246] In the same manner as in Example 1, except that the resin layer(X′-4-3) was bonded in place of the resin layer (X-1), the same member(K-4) (41) as the member (K-1) in Example 1, bonding was performed usingan adhesive resin layer (42).

[0247] Formation of Inlet and Outlet Portions

[0248] At both ends of the cut portion (33′) of the resin layer(X′-4-1), an orifice having a diameter of 1.6 mm was made in the basematerial (35) and the resin layer (36) using a drill and a stainlesssteel pipe having a diameter of 1.6 mm was bonded to form an inlet (43)and an outlet (44), which communicate with the cut portion (33′) of theresin layer (X′4-1). Also, at both ends of the cut portion (34′) of theresin layer (X′-4-1), an orifice having a diameter of 1.6 mm was made inthe base material (35) and the resin layer (36) using a drill and astainless steel pipe having a diameter of 1.6 mm was bonded to form aninlet (45) and an outlet (46), which communicate with the cut portion(34′) of the resin layer (X′-4-1), to manufacture a microdevice (D-4).

[0249] Water Flow Test

[0250] Dye-colored water introduced from the inlet portion (45) flowedout through the liquid outlet portion (46) via cut portions (34′),(38′), (40′), (38′) and (34′), while distilled water introduced throughthe inlet portion (43) flowed out through the outlet portion (44) viathe cut portion (33′) without mixing with the dye-colored water. As aresult, it was confirmed that two independent passages intersectthree-dimensionally.

Example 5

[0251] In this Example, a method of manufacturing a microdevice having adiaphragm valve function will be described.

[0252] Formation of Member (J-5-1)

[0253] In the very same manner as in the case of the member (J-1)manufactured in Example 1, a member (J-5-1) wherein a resin layer (55)having no cut portion is formed on a base material (54) made ofpolystyrene was manufactured.

[0254] Formation of Resin Layer (X-5-1)

[0255] In the same manner as in the case of the formation of the resinlayer (X-1) in Example 1, except that the non-exposure portion has adifferent width, a resin layer (X-5-1) (52) having a cut portion (53′)of about 200 μm in width was formed on the surface of the member (J-5-1)to manufacture a member (J-5-2).

[0256] Formation of Intermediate Layer

[0257] In the same manner as in the case of the formation of the resinlayer (X-1) in Example 1, except that the member (J-5-2) was used inplace of the member (J-1) and the composition (x-3) was used in place ofthe composition (x-1) and, furthermore, the entire surface wasirradiated without using a photomask during the exposure, anintermediate layer (56) having no cut portion was formed on the resinlayer (X-5-1).

[0258] Formation of Resin Layer (X-5-2)

[0259] In the same manner as in the case of the formation of the resinlayer (X-1) in Example 1, except that a member (J-5-3) was used in placeof the member (J-1) and the shape of the non-exposure portion is apattern composed of a circular portion having a diameter of 1 mm at acenter and a linear portion having a length of 15 mm and a width of 200μm connected with the circular portion, which form a cut portion (58′)as shown in FIG. 9, a resin layer (X-5-2) (57) was formed on theintermediate layer (56) to manufacture a member (J-5-4).

[0260] Bonding of Member (K-5)

[0261] In the same manner as in the case of the bonding of the member(K-1) in Example 1, except that the member was bonded with the resinlayer (X-5-2) in place of the resin layer (X-1), the same member (K-5)(59) as the member (K-1) was bonded with the member (J-5-4) via anadhesive resin layer (60).

[0262] Formation of Inlet and Outlet

[0263] At both ends of the cut portion (53′) of the resin layer (X-5-1),an orifice having a diameter of 5.1 mm was made in the member (J-5-1)using a drill and a vinyl chloride pipe having an outer diameter of 5 mmwas bonded using an epoxy adhesive to form a liquid inlet portion (61)and a liquid outlet portion (62), which communicate with the cut portion(53′) of the resin layer (X′-5-1).

[0264] Also, at the external end of the cut portion (58′) of the resinlayer (X-5-2), an orifice having a diameter of 1.6 mm was made in thebase material (59) and the resin layer (60) of the member (K-5) using adrill and a stainless steel pipe having an outer diameter of 1.6 mm wasbonded using an epoxy adhesive to form a gas inlet portion (63) whichcommunicates with the cut portion (58′) of the resin layer (X-5-2) (57),thereby manufacturing a microdevice (D-5). A plan view schematicallyshowing the microdevice thus manufactured is shown in FIG. 9 and asectional view taken along line A-A in FIG. 9 is shown in FIG. 10.

[0265] Flow Rate Control Test

[0266] Water was introduced through a liquid inlet portion (61) under apressure of about 10 kPa. While maintaining the state where water flowsthrough a liquid outlet portion (62) open to the air, nitrogen at apressure of 0.5 MPa was introduced from a gas introduction portion (63).As a result, the flow rate of water became zero. The flow rate of watercould be controlled by changing the nitrogen pressure. Thus, it wasconfirmed that the microdevice can operate as an on-off valve and a flowrate control valve.

Example 6

[0267] In this Example, a method of manufacturing a microdevice of thepresent invention, which has a configuration such that the resin layer(X′) is interposed between the member (J′) and the member (K′) eachhaving a groove using the method of the present invention wherein thecoating substrate is removed by dissolution will be described.

[0268] Manufacture of Coating Substrate

[0269] On the surface subjected to a corona discharge treatment of a 30μm thick biaxially stretched polypropylene film (OPP film, manufacturedby Futamura Chemical Industries Co., Ltd.), one surface of which issubjected to a corona discharge treatment, an aqueous 20% solution ofpolyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.,polymerization degree: 2000) was applied and hot air-dried at 40° C. andthen vacuum-dried at 40° C. After peeling off from the OPP film, apolyvinyl alcohol film was formed, thereby manufacturing a coatingsubstrate.

[0270] Manufacture of Member (J′-6)

[0271] Using the same melt replica method as in Example 2, a member(J′-6) having a recessed portion, which has a configuration such thatthe polystyrene plate (4) in Example 1, the resin layer (5) having nocut portion and the resin layer (X-1) having three linear cut portionsshown in FIG. 4 are laminated.

[0272] Manufacture of Resin Layer (X′) Precursor

[0273] In the same manner as in the steps (i), (ii) and (iii) of Example2, except that the coating substrate is a polyvinyl alcohol film and theshape, which serves as the cut portion, is the same as those of twoorifice-shaped cut portion (38) shown in FIG. 5, a semi-cured coatingfilm was formed.

[0274] After the semi-cured coating film formed on the coating substratewas laminated with the member (J′-6), the coating substrate wasdissolved and removed by washing with running water at 400 C to form aresin layer (X′-6) precursor laminated with the member (J′-6) in asemi-cured state (steps (iv) and (v)).

[0275] Manufacture of Member (K′)

[0276] In the same manner as in the case of the member (J′-6), exceptthat the shape of the recessed cut portion on the surface is the same asthat of the cut portion shown in FIG. 6, a member (K′-6) wasmanufactured.

[0277] Lamination and Bonding of Member (K′)

[0278] On the resin layer (X′-6) precursor, the member (K′-6) waslaminated and then irradiated with ultraviolet light for 40 seconds(step (vi)), thereby curing the resin layer (X′-6) precursor and bondingthe member (J′-6) and the member (K′-6) with the resin layer (X′-6).

[0279] Formation of Other Structures

[0280] In the same manner as in Example 1, a stainless steel pipe wasbonded to the end of each respective passage to form an inlet portionand an outlet portion, thereby manufacturing a microdevice (D-6) havingthe same passage structure as that of the microdevice (D-4) shown inFIG. 7 and FIG. 8.

Example 7

[0281] In this Example, an example of manufacturing a microdevice of thepresent invention, wherein two resin layers (X′) are laminated with themember (J′) having a groove on the surface, by the method of the presentinvention, wherein the coating substrate is removed by dissolution, willbe described.

[0282] Coating Substrate, Member (J′-7)

[0283] In the same manner as in Example 6, a coating substrate of apolyvinyl alcohol film was manufactured. As the member (J′), the samemember as the member (J′-6) in Example 6 was used to manufacture amember (J′-7-1).

[0284] Manufacture of Member (J′-7-1)-Resin Layer (X′-7-1) Laminate

[0285] In the very same manner as in Example 6, the very same member asthat of the member (J′-6) and the resin layer (X′-6) laminate, alaminate of the member (J′-7-1) and the resin layer (X′-7-1) precursorwas manufactured.

[0286] Formation of Resin Layer (X′-7-2)

[0287] Using the same operation as described above, except that thelaminate of the member (J′-7-1) and the resin layer (X′-7-1) precursorwas used as a member (J′-7-2) and the shape of the cut portion is thesame as that of the recessed cut portion of the member (K′-6) in Example6, the resin layer (X′-7-2) precursor was laminated on the resin layer(X′-7-1) precursor to manufacture a member (J′-7-2).

[0288] Lamination and Bonding of Member (K′-7)

[0289] Using the polystyrene plate used in Example 6 as the member(K′-7), the member was laminated on the resin layer (X′-7-2) precursor,and then irradiated with ultraviolet light for 40 seconds, therebycuring resin layer (X′-7-1) precursor and resin layer (X′-7-2) precursorand bonding the member (J′-7), the resin layer (X′-7-1), the resin layer(X′-7-2) and the member (K′-7).

[0290] Formation of Other Structures

[0291] In the same manner as in Example 1, a stainless steel pipe wasbonded to the end of each respective passage to form an inlet portionand an outlet portion, thereby manufacturing a microdevice (D-7) havingthe same passage structure as that of the microdevice (D-4) shown inFIG. 7 and FIG. 8.

Example 8

[0292] In this Example, an example of manufacturing a microdevice of thepresent invention which has a stopper and which functions as a pump bythe method of the present invention will be described.

[0293] Manufacture of Member (J′-8-1)

[0294] A semi-cured coating film (72) having no cut portion was formedby applying a composition (x-1′) on a plate having dimensions of 5 cm×5cm×3 mm (thickness) made of polystyrene (“DICSTYRENE XC-520”,manufactured by Dainippon Ink and Chemicals, Inc.) as a base material(71) and irradiating with ultraviolet light without using a photomaskfor one second.

[0295] Furthermore, a composition (x-1) was applied thereon and theportion other than the portion, which serves as a cut portion (74) shownin FIG. 11, was irradiated with ultraviolet light for 3 seconds using aphotomask. Then, the uncured composition (x-1) of the non-irradiatedportion was removed using methanol to form a resin layer (73) on whichtwo recessed cut portions (74) and (74′), each having a width of 100 μmand a length of 10 mm, are arranged in series at a interval of 0.6 mm asthe cut portion of the coating film. At both ends of the recessed cutportions (74) and (74′) of the laminate, through holes (75) and (75′),each having a diameter of 3 mm, were made to manufacture a member(J′-8-1).

[0296] Formation of Resin Layer (X′-8-1)

[0297] In the same manner as in Example 1, except that the shape, whichserves as-the cut portion, is in the form of two orifices (77) and(77′), each having a diameter of 100 μm and a diameter of 600 μm,arranged at a center distance of 1 mm as shown in FIG. 12, a resin layer(X′-8-1) (76) including a cut portion having the above shape waslaminated on the member (J′-8-1) by a method of peeling a coatingsubstrate to manufacture a member (J′-8-2).

[0298] Formation of Resin Layer (X′-8-2)

[0299] In the same manner as in Example 6, except that a composition(x-3) was used as the composition (x) and the shape, which serves as acut portion, is in the form of horseshoes (79) and (79′), each having aperipheral width of 100 μm, arranged in a center distance of 1 mm asshown in FIG. 13, the horseshoes serving as tongue-shaped stoppers (80)and (80′), each having a diameter of 400 μm, a semi-cured coating filmwas formed on a coating substrate (not shown).

[0300] Using a photomask, only portions, which serve as thetongue-shaped stoppers (80) and (80′), surrounded with thehorseshoes-shaped cut portions (79) and (79′) were further irradiatedwith ultraviolet light for 20 seconds, thereby curing the composition(x-3) of the irradiated portion and maintaining the other portion in asemi-cured state (step (iii′)). In the same manner as in Example 6, alaminate, wherein a resin layer (X′-8-2) (78) is laminated on the member(J′-8-2), was obtained by the method of removing the coating substrateby dissolution to manufacture a member (J′-8-3).

[0301] Formation of Resin Layer (X′-8-3)

[0302] On the resin layer (X′-8-2) of the member (J′-8-3), a resin layer(X′-8-3) (81) formed in the same manner as in the case of the resinlayer (X′-8-1) (76), except that positions of two orifices (82) and(82′) having different sizes are reverse to those of two orifices (77)and (77′) having different sizes of the resin layer (X′-8-1) (76) waslaminated to manufacture a member (J′-8-4).

[0303] Formation of Resin Layer (X′-8-4)

[0304] In the same manner as in the case of the resin layer (X′8-1)(76), except that the shape of the cut portion (84) is a linear shapehaving a length of 1.5 mm and a width of 700 μm as shown in FIG. 14, aresin layer (X′-8-4) (83) was laminated on the resin layer (X′-8-3) (81)of the member (J′-8-4) to manufacture a member (J′-8-5).

[0305] Formation of Intermediate Layer

[0306] In the same manner as in the case of the formation of theintermediate layer (56) in Example 5, except that a member (J′-8-5) wasused in place of the member (J′-5-2), an intermediate layer (85)(diaphragm layer) having no cut portion formed of a flexible materialwas laminated and bonded on the resin layer (X′-8-4).

[0307] Manufactured and Bonding of Member (K′-8)

[0308] As shown in FIG. 16, a member (K′-8), which is the same as themember (J′-8-1), except that the shape of the recessed cut portion (88)is a T-shape composed of a line having a length of 1.5 mm and a width of700 μm and a line having a length of 10 mm and a width of 300 μm and oneorifice-shaped cut portion (89) piercing through the member is providedat the end of a recessed cut portion having a width of 300 μm, wasmanufactured in the same manner as in the case of the member (J′-8-1).The member (K′-8) is formed as a laminate of a base material (86) madeof polystyrene and a resin layer (87) having the cut portion (88).

[0309] The member (K′-8) was laminated on the intermediate layer (85)while aligning the cut portion (88) of the member with the positioncorresponding to the cut portion (84) of the resin layer (X′-8-4) acrossthe intermediate layer (85), and then irradiated with ultraviolet lightfor 30 seconds, thereby bonding with the intermediate layer (85), tomanufacture a diaphragm. Also, the other resin layer was sufficientlycured by irradiation with ultraviolet light.

[0310] Formation of Inlet and Outlet Portions

[0311] A vinyl chloride pipe having an outer diameter was bonded withorifices (75), (75′) and (89) provided on the member (J′8) and themember (K′-8) using an epoxy adhesive to form a liquid inlet portion(90), a liquid outlet portion (91) and a gas introduction portion (92),thereby manufacturing a microdevice (D-8). A plan view schematicallyshowing the microdevice thus manufactured is shown in FIG. 17 and anelevation view schematically showing the microdevice is shown in FIG.18.

[0312] Liquid Delivery Test

[0313] Water was introduced through a liquid inlet portion (90). As aresult, water flowed out through a liquid outlet portion (91) open tothe air. In contrast, even if water was introduced into the liquidoutlet portion (91), water did not flow out through the liquid inletportion (90). Then, nitrogen at 0.5 MPa was intermittently introducedinto the liquid inlet portion (92). As a result, water was drawn throughthe liquid inlet portion (90) and flowed out through liquid inletportion (91). Thus, it was confirmed that the microdevice operated as apump.

Example 9

[0314] In this Example, an example of a microdevice having a diaphragmvalve function, which has a structure such that the diaphragm is notbonded but is contacted with the adjacent member, and a method ofmanufacturing the same will be described.

[0315] Manufacture of Microdevice

[0316] In the same manner as in Example 5, except that the shape of thenon-irradiated portion of the resin layer (X-5-1) is in the form of twoorifices corresponding to the liquid inlet portion (61) and the liquidoutlet portion (62) and the portion corresponding to the non-irradiatedportion of the resin layer (X-5-1) in Example 5, was cured byirradiating with ultraviolet light after the removal of the uncuredresin of the non-irradiated portion of the resin layer (X-5-1) andbefore laminating the intermediate layer (56), and that the portion,which severs as the diaphragm of the intermediate layer (56), that is,the shape of the cavity (53) of Example 5 was irradiated withultraviolet light, thereby curing the irradiated portion, and theintermediate layer (56) corresponds to the member (K″) in themicrodevice of the present invention, the same microdevice as thatmanufactured in Example 5, except that the cavity (53) of Example 5 hasa zero thickness, was manufactured.

[0317] Water Flow Test

[0318] Water was introduced through a liquid inlet portion (61) under apressure of about 5 kPa. As a result, water did not flow through aliquid outlet portion (62) open to the air. The pressure increased to 15kPa, water flowed out through the liquid outlet portion (62). Whilemaintaining this state, nitrogen at a pressure of 0.5 MPa was introducedfrom a gas introduction portion (63). As a result, the flow rate ofwater became zero. The flow rate of water could be controlled bychanging the nitrogen pressure. Thus, it was confirmed that themicrodevice can operate as a check valve, an on-off valve, and a flowrate control valve.

INDUSTRIAL APPLICABILITY

[0319] The present invention can provide a method of manufacturing amicrodevice having a fine capillary cavity formed as a cut portion of avery thin layer which is likely to be broken, particularly a method ofmanufacturing a microdevice having complicated passages formed in threedimensions with high productivity, and a multi-functional microdevicewhich has a fine capillary passage formed by laminating plural resinlayers, fine capillary cavities piercing through the respective layersto communicate and intersect three-dimensionally with each other, aspace which should serve as a reaction chamber, a diaphragm valve, and astopper structure.

1. A method of manufacturing a microdevice having a laminated structurecomprising one or more resin layers (X) having a cut portion, said resinlayers being laminated with another member or another resin layer (X) toform a cavity composed of the cut portion, said method comprising: (i)the step (i) of applying an active energy ray curable composition (x)containing a radiation polymerizabie compound (a) on a coating substrateto form an uncured coating film, (ii) the step (ii) of irradiating theuncured coating film other than the portion, which should serve as thecut portion, with an active energy ray, thereby making the uncuredcoating film of the irradiated portion non-flowable or slightlyflowable, and semi-curing to such an extent that unreacted active energyray polymerizable functional groups can remain to form a semi-curedcoating film, (iii) the step (iii) of removing the uncured composition(x) of the non-irradiated portion from the semi-cured coating film toobtain a semi-cured coating film having a cut portion of the coatingfilm, (iv) the step (iv) of laminating the semi-cured coating filmhaving a cut portion with another member (J) to form a resin layer (X),(v) the step (v) of removing the coating substrate from the resin layer(X), thereby transfering the resin layer (X) onto the member (J), and(vi) the step (vi) of irradiating the resin layer (X) in a semi-curedstate with an active energy ray, thereby further curing the resin later(X) and bonding the resin layer (X) with the member (J) after the step(iv) and before and/or after the step (v).
 2. The method ofmanufacturing a microdevice according to claim 1, wherein the removal ofthe coating substrate in the step (v) is removal by dissolution of thecoating substrate.
 3. The method of manufacturing a microdeviceaccording to claim 1, wherein the step (vi) is provided before the step(v) and the removal of the coating substrate in the step (v) isperformed by peeling.
 4. The method of manufacturing a microdeviceaccording to claim 1, wherein, after performing the steps (i), (ii),(iii), (iv) and (v), or the steps (i), (ii), (iii), (iv), (v) and (vi),or the steps (i), (ii), (iii), (iv), (vi) and (v) in this order, thesteps (i) to (v) or the steps (i) to (vi) are repeated using the member(J) laminated with the resin layer (x) in place of the member (J) in thestep (iv), thereby laminating plural resin layers (X).
 5. The method ofmanufacturing a microdevice according to claim 1, wherein plural resinlayers (X) are laminated so that at least the cut portions are partiallylaid one upon another to form a cavity composed of the connected cutportions of plural resin layers (X) in a laminate.
 6. The method ofmanufacturing a microdevice according to claim 1, wherein the member (J)is a member having a cut portion piercing through the member, or amember having a recessed cut portion on the surface, or a member havinga cut portion piercing through the member and a recessed cut portion onthe surface, and the member (J) and the resin layer (X) are laminated sothat at least the cut portion of the member (J) and the cut portion ofthe resin layer (X) are partially laid one upon another to form a cavitycomposed of the cut portion of the member (J) and the cut portion of theresin layer (X), which are connected with each other, in a laminate. 7.The method of manufacturing a microdevice according to claim 1, whereinthe step (vi) follows the step (v) and, in the step (vi), the resinlayer (X) in a semi-cured state is irradiated with an active energy raywhile being contacted with another member (K), thereby bonding the resinlayer (X) with the member (J) and bonding with the another member (K).8. The method of manufacturing a microdevice according to claim 7,wherein the member (K) has a cut portion piercing through the memberand/or a recessed cut portion on the surface and the member (K) and theresin layer (X) are laminated so that the cut portion of the member (K)and the cut portion of the resin layer (X) are partially laid one uponanother, thereby forming a cavity composed of the cut portion of themember (K) and the cut portion of the resin layer (X), which areconnected with each other, in a laminate.
 9. The method of manufacturinga microdevice according to claim 1, wherein, between the step (i) andthe step (ii) and/or between the step (ii) and the step (iii) and/orbetween the step (iii) and the step (iv), a portion of the resin layer(X) is irradiated with an active energy ray, thereby partially curingthe resin layer so-that the irradiated portion is not bonded withanother member in the step (iv) to form a portion, which is not bondedbut is contacted with the another member or resin layer, in the resinlayer (X).
 10. The method of manufacturing a microdevice according toclaim 9, wherein irradiation with the active energy ray in the step (ii)is performed in the shape for forming a stopper to provide a portion ofthe resin layer (X) with a structure, which serves as the stopper, andthe portion subjected to partial curing is a portion which serves as thestopper of the resin layer (X).
 11. The method of manufacturing amicrodevice according to claim 1, wherein a thickness of the resin layer(X) is within a range from 1 to 1000 μm.
 12. The method of manufacturinga microdevice according to claim 1, wherein a minimum width of the cutportion of the resin layer (X) is within a range from 1 to 1000 μm. 13.The method of manufacturing a microdevice according to claim 1, whereinthe radiation polymerizable compound (a) is a compound having two ormore active energy ray polymerizable functional groups in a molecule.14. The method of manufacturing a microdevice according to claim 13,wherein the radiation polymerizable compound (a) having an acryloylgroup or a maleimide group.
 15. The method of manufacturing amicrodevice according to claim 1, wherein the active energy ray curablecomposition (x) contains a hydrophobic radiation polymerizable compound(a) whose homopolymer exhibits a contact angle with water of 60 degreesor more, and an amphipathic polymerizable compound (b) which iscopolymerizable with the hydrophobic radiation polymerizable compound.16. The method of manufacturing a microdevice according to claim 15,wherein the amphipathic polymerizable compound (b) is a compound havinga polyethylene glycol chain of a repeating number of 6 to 20 and analkyl group having 6 to 20 carbon atoms in the molecule.
 17. The methodof manufacturing a microdevice according to claim 1, wherein the member(J) is formed of a polymer selected from the group consisting of styrenepolymer, (meth)acrylate polymer, polycarbonate polymer, polysulfonepolymer and polyester polymer.
 18. A microdevice having a laminatedstructure comprising a member (J′) {selected from a member having a cutportion piercing through the member, a member having a recessed cutportion on the surface, and a member having a cut portion piercingthrough the member and a recessed cut portion on the surface}, one ormore active energy ray curable resin layers (X′) having a cut portion ata portion of the layer, the cut portion having a minimum width within arange from 1 to 1000 μm, and a member (K′) {selected from a memberhaving a cut portion piercing through the member, a member having arecessed cut portion on the surface, and a member having a cut portionpiercing through the member and a recessed cut portion on the surface},which are laminated, while two or more cut portions in the members areconnected to form a cavity.
 19. The microdevice according to claim 18,wherein one or more members selected from the member (J′), the resinlayer (X′) and the member (K′) has one or more linear cavity providedparallel to the laminated surface of the members.
 20. The microdeviceaccording to claim 18, wherein a thickness of the resin layer (X′)having a cut portion is within a range from 5 to 1000 μm.
 21. Themicrodevice according to claim 18, wherein a portion of the cavity is afluid passage and plural passages formed in different resin layers (X′)or branched passages intersect three-dimensionally across the resinlayer (X′).
 22. The microdevice according to claim 18, which has aportion that is not bonded but is contacted with another memberlaminated adjacent to a portion of one or more members selected from themember (J′), the resin layer (X′) and the member (K′).
 23. Themicrodevice according to claim 22, wherein a portion of at least oneresin layer (X′) is provided with a structure, which serves as a stopperby replacing a portion of the peripheral portion by a cut portion andthe portion, which is not bonded but is contacted with the anothermember laminated adjacent thereto, is a stopper.
 24. The microdeviceaccording to claim 23, wherein two or more structures, which serve as astopper, are provided in one resin layer (X′).
 25. The microdeviceaccording to claim 22, wherein the resin layer (X′) provided with thestructure, which serves as a stopper, is formed of a material having alower tensile elasticity than that of the members or resin layersbetween which the structure is interposed.
 26. The microdevice accordingto claim 18, wherein the active energy ray curable resin layer (X′) is acured article of an active energy ray curable composition containing a(meth)acryloyl group-containing compound.
 27. The microdevice accordingto claim 18, wherein at least one member selected from the member (J′),the resin layer (X′) and the member (K′) is directly laminated with amember, which serves as a diaphragm, at one surface and is directlylaminated with another member having a cut portion at the other surface,and the cut portions form a cavity by lamination, while another memberlaminated on the back surface of the member, which serves as thediaphragm, has orifice-shaped cut portions, which serve as an inletand/or an outlet to the cavity, at least one of the inlet and the outletbeing formed across the member from the diaphragm, and the peripheralportion does not contact with the diaphragm and the passage can beclosed by deforming the diaphragm to contact with the peripheral portionof at least one of the inlet and the outlet.
 28. The microdeviceaccording to claim 18, wherein the active energy ray curable compositioncontains an amphipathic radiation polymerizable compound which iscopolymerizable with a radiation polymerizable compound.
 29. Themicrodevice according to claim 28, wherein the amphipathic polymerizablecompound is a compound having a polyethylene glycol chain of a repeatingnumber of 6 to 20 and an alkyl group having 6 to 20 carbon atoms in themolecule.
 30. The microdevice according to claim 18, wherein a portionor all of the cavity is a fluid passage.
 31. A microdevice wherein amember (J′) {selected from a member having a cut portion piercingthrough the member, a member having a recessed cut portion on thesurface, and a member having a cut portion piercing through the memberand a recessed cut portion on the surface}, one or more active energyray curable resin layers (X′) having a cut portion at a portion of thelayer, the cut portion having a minimum width within a range from 1 to1000 μm, and a member (K″) having no cut portion, which serves as adiaphragm, are laminated and the member (K″) has a portion, which is notbonded but is contacted with another member laminated adjacent thereto,the portion being a diaphragm portion, while two or more cut portions inthe member (J′) and the resin layer (X′) are connected to form a cavity.32. The microdevice according to claim 31, wherein the cut portions ofone or more members of the member (J′) and the resin layer (X′) areorifice-shaped cut portions, which serve as an inlet and/or an outlet,at least one of the inlet and the outlet being formed across the memberfrom the diaphragm, and the peripheral portion does not contact with thediaphragm and the passage can be opened by deforming the diaphragm tocontact with the peripheral portion of at least one of the inlet and theoutlet.
 33. The microdevice according to claim 27, 31 or 32, wherein adiaphragm is formed of a material having a thickness within a range from1 to 500 μm and a tensile elasticity within a range from 1 to 700 MPa.34. A microdevice manufactured by the method of any one of claims 1 to17.